Ester derivative, liquid crystal composition and liquid crystal display element

ABSTRACT

A novel liquid crystalline compound having a large dielectric anisotropy value, a small change in the threshold voltage depending upon temperatures, and an improved solubility in other liquid crystal materials at low temperatures, and a liquid crystal composition containing the compound are provided, 
     which liquid crystalline compound is expressed by the formula (1) ##STR1##  wherein R is H or an alkyl group of 1 to 10C; l is an integer of 1 to 9; m, n and o are each independently 0 or 1; A 1 , A 2  and A 3  are each independently trans-1,4-cyclohexylene group, 1,4-phenylene group, one or more H atoms on the ring of which group may be replaced by F, or the like group; Z 1 , Z 2  and Z 3  are each independently --COO--, etc., but at least one of them is --COO--; X is CF 3 , etc.; and Y 1 , and Y 2  are each independently H or F.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a liquid crystalline compound and a liquidcrystal composition, and more particularly, it relates to a novel estercompound having a 4-substituted phenyl group, a 3-fluoro-4-substitutedphenyl group or a 3,5-difluoro-4-substituted phenyl group, a liquidcrystal composition containing the compound, and a liquid crystaldisplay element containing the liquid crystal composition.

2. Description of the Related Art

Display elements using liquid crystalline compounds have been broadlyutilized for watch, electric calculator, word processor, etc. Thesedisplay elements are those utilizing the optical anisotropy, dielectricanisotropy, etc. of liquid crystalline compounds.

Liquid crystal phases include nematic liquid crystal phase, smecticliquid crystal phase and cholesteric liquid crystal phase, and amongthese, materials utilizing nematic liquid crystal phase have been mostbroadly used. Further, display modes include dynamic scattering (DS)mode, deformation of vertical aligned phase (DAP) mode, guest-host (GH)mode, twisted nematic (TN) mode, super-twisted nematic (STN) mode,thin-film transistor (TFT) mode, etc.

Liquid crystalline compounds used in these display modes must exhibitliquid crystal phases within a broad temperature range around roomtemperature, have a sufficient stability under conditions under whichdisplay elements are used, and have characteristics sufficient fordriving display elements, but at present, a single liquid crystallinecompound satisfying these conditions has not yet been found. Thus, it isan actual state that liquid crystal compositions provided with requiredcharacteristics have been prepared by blending liquid crystallinecompounds of several kinds to several tens of kinds and if necessary,further non-liquid crystalline compounds. It is required for theseliquid crystal compositions to be stable to light, heat and air whichare usually present under conditions wherein display elements are used,and further to be stable to electric field or electromagneticirradiation, and still further to be chemically stable to compounds tobe blended. Further, it is required for liquid crystal compositions thatthe values of various physical properties such as optical anisotropyvalue (Δn), dielectric anisotropy value (Δε), etc. are suitable,depending upon the display mode and the shape of the display element.Further, the respective components in the liquid crystal compositionsare important to have a good compatibility with each other.

Among these requirements, there has been increasing a requirement forfurther reduction in the threshold voltage greatly contributing to ahigh speed response necessary for making a large picture surface ofliquid crystal display elements. A liquid crystalline compound having alarge Δε value is necessary therefor. (E. Jakeman et al, Phys. Lett.,39A. 69 (1972)).

Further, in order to make a high picture surface quality possible, aliquid crystalline compound having a small change in the thresholdvoltage depending upon temperatures is needed.

In order to achieve these objects, compounds of the formulas (a) and (b)are respectively disclosed in Japanese patent application Hyo No. Hei3-503637 and Japanese patent application laid-open No. Hei 4-279560.Further, compounds disclosed in Japanese patent application laid-openNo. Sho 55-40660, Japanese patent application Hyo No. Hei 2-501311, andJapanese patent application Hyo No. Hei 3-500413 are known.

However, these compounds have problems that change in the thresholdvoltage depending upon temperatures can not be yet regarded as beingsufficiently small and further the solubility thereof in liquid crystalcompositions at low temperatures is insufficient.

SUMMARY OF THE INVENTION

The object of the present invention is to provide an ester compoundwhich has overcome the above drawbacks of the prior art, and has aparticularly large Δε, a small change in the driving voltage dependingupon temperatures, and an improved solubility in other liquid crystalcompositions at low temperatures; a liquid crystal compositioncontaining the above compound; and a liquid crystal display elementcomposed using the liquid crystal composition.

The present invention has the following aspects of items (1) to (13):

(1) A liquid crystalline compound expressed by the formula (1): ##STR2##wherein R represents an alkyl group of 1 to 10 carbon atoms; lrepresents an integer of 1 to 9; m, n and o each independently represent0 or 1; A₁, A₂ and A₃ each independently representtrans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diylgroup, pyridine-2,5-diyl group or 1,3-dioxane-2,5-diyl group, one ormore hydrogen atoms on the rings of which groups may be replaced by F;Z₁, Z₂ and Z₃ each independently represent --COO--, --(CH₂)₂ -- or acovalent bond at least one of which represents --COO--; X represents CN,CF₃, CF₂ H, CFH₂, OCF₃ or OCF₂ H; Y₁ and Y₂ each independently representH or F, but when X represents CN, Y₁ and Y₂ both represent F.

(2) A liquid crystalline compound according to item (1), wherein mrepresents 1; n and o represents 0; A₁ represents 1,4-phenylene group,one or more hydrogen atoms on the ring of which group may be replaced byF; and Z₁ represents --COO--.

(3) A liquid crystalline compound according to item (1), wherein m and neach represent 1; o represents 0; A₁ and A₂ each represent 1,4-phenylenegroup, one or more hydrogen atoms on the ring of which group may bereplaced by F; and Z₁ represents --COO--.

(4) A liquid crystalline compound according to item (1), wherein m and neach represent 1; o represents 0; A₁ represents 1,4-phenylene group, oneor more hydrogen atoms on the ring of which group may be replaced by F;A₂ represents trans-1,4-cyclohexylene group; and Z₁ represents --COO--.

(5) A liquid crystalline compound according to item (1), wherein m and neach represent 1; o represents 0; A₁ represents trans-1,4-cyclohexylenegroup; A₂ represents 1,4-phenylene group, one or more hydrogen atoms onthe ring of which group may be replaced by F; and Z₂ represents --COO--.

(6) A liquid crystalline compound according to item (1), wherein m and neach represent 1; o represents 0; A₁ and A₂ each represent 1,4-phenylenegroup, one or more hydrogen atoms on the ring of which group may bereplaced by F; and Z₂ represents --COO--.

(7) A liquid crystalline compound according to item (1), wherein m and neach represent 1; o represents 0; A₁ represents trans-1,4-cyclohexylene;A₂ represents 1,4-phenylene group, one or more hydrogen atoms on thering of which group may be replaced by F; Z₁, represents --(CH₂)--; andZ₂ represents --COO--.

(8) A liquid crystalline compound according to item (1), wherein m, nand o each represent 1; A₁, represents trans-1,4-cyclohexylene group; A₂and A₃ each represent 1,4-phenylene group,one or more hydrogen atoms onthe ring of which group may be replaced by F; Z₁, and Z₃ each representa covalent bond; and Z₂ represents --COO--.

(9) A liquid crystal composition characterized by containing at leastone member of the liquid crystalline compound set forth in either one ofitems (1) to (8).

(10) A liquid crystal composition characterized by containing as a firstcomponent, at least one member of the liquid crystalline compounds setforth in either one of items (1) to (8), and as a second component, atleast one member selected from the group consisting of compoundsexpressed by the following formulas (2), (3) and (4): ##STR3##

In these formulas, R₁ represents an alkyl group of 1 to 10 carbon atoms;X₁ represents F, Cl, OCF₃, OCF₂ H, CF₃, CF₂ H or CFH₂ ; L₁, L₂, L₃ andL₄ each independently represent H or F; Z₄ and Z₅ each independentlyrepresent --(CH₂)₂ --, --CH═CH-- or a covalent bond; and a represents 1or 2.

(11) A liquid crystal composition characterized by containing as a firstcomponent, at least one member of the liquid crystalline compounds setforth in either one of items (1) to (8), and as a second component, atleast one member selected from the group consisting of compoundsexpressed by the following formulas (5), (6), (7), (8) and (9): ##STR4##

In the formula (5), R₂ represents F, an alkyl group of 1 to 10 carbonatoms or an alkenyl group of 2 to 10 carbon atoms, and an optionalmethylene group (--CH₂ --) in the alkyl group or the alkenyl group maybe replaced by oxygen atom (--O--), but two or more methylene groups arenot successively replaced by oxygen atom; ring A representstrans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diylgroup or 1,3-dioxane-2,5-diyl group; ring B representstrans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring C represent trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₆ represents --(CH₂)₂ --, --COO-- or acovalent bond; L₅ and L₆ each independently represent H or F; b and ceach independently represent 0 or 1.

In the formula (6), R₃ represents an alkyl group of 1 to 10 carbonatoms; L₇ represents H or F; and d represents 0 or 1.

In the formula (7), R₄ represents an alkyl group of 1 to 10 carbonatoms; rings D and E each independently representtrans-1,4-cyclohexylene group or 1,4-phenylene group; Z₇ and Z₈ eachindependently represent --COO-- or a covalent bond; Z₉ represents--COO-- or --C.tbd.C--; L₈ and L₉ each independently represent H or F;X₂ represents F, OCF₃, OCF₂ H, CF₃, CF₂ H or CFH₂, but when X2represents OCF₃, OCF₂ H₂, CF₃, CF₂ H or CFH₂, L₈ and L₉ both representH; and e, f and g each independently represent 0 or 1.

In the formula (8), R₅ and R₆ each independently represent an alkylgroup of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbonatoms, and in either of the groups, an optional methylene group (--CH₂--) may be replaced by oxygen atom (--O--), but two or more methylenegroups are not continuously replaced by oxygen atom; ring G representstrans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring H represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₁₀ represents --C.tbd.C--, --COO--,--(CH₂)₂ --, --CH═CH--C.tbd.C-- or a covalent bond; and Z₁₁ represents--COO-- or a covalent bond.

In the formula (9), R₇ and R₈ each independently represent an alkylgroup of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbonatoms, and in either of the groups, an optional methylene group (--CH₂--) therein are not continuously replaced by oxygen atom; ring Irepresents trans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring J represents trans-1,4-cyclohexylenegroup, or 1,4-phenylene group, or pyrimidine-2,5-diyl group, one or morehydrogen atoms on the rings of which groups may be replaced by F, ring Krepresents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z₁₂ andZ₁₄ each independently represent --COO--, --(CH₂)₂ -- or a covalentbond; Z₁₃ represents --CH═CH--, --C.tbd.C--, --COO-- or a covalent bond;and h represents 0 or 1.

(12) A liquid crystal composition, characterized by containing as afirst component, at least one member of the liquid crystalline compoundsset forth in either one of items (1) to (8), as a part of a secondcomponent, at least one member selected from the group consisting of thecompounds expressed by the formulas (2), (3) and (4) set forth in item(10), and as another part of the second component, at least one memberselected from the group consisting of the compounds expressed by theformulas (5), (6), (7), (8) and (9) set forth in item (11).

(13) A liquid crystal display element composed of a liquid crystalcomposition set forth in either one of items (9) to (12).

(14) A phenol derivative as a raw material for a liquid crystallinecompound, expressed by the formula (1-a): ##STR5## wherein A₃ representstrans-1,4-cyclohexylene group or 1,4-phenylene group one or more ofhydrogen atoms on the ring of which group may be replaced by F, Xrepresents CF₃, CF₂ H, CFH₂, OCF₃ or OCF₂ H, Y₁ represents H or F, orepresents an integer of 0 or 1, but when o represents 0, and Xrepresents CF₃, Y₁ represents H.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

FIG. 1 is a graph for explaining the effectiveness of a liquid crystalcomposition as an example of the present invention.

FIG. 2 is a graph explaining the effectiveness of another liquid crystalcomposition of the present invention.

Descriptions of the symbols in the drawings:

(a) A liquid crystal composition of the present invention.

(b) Another liquid crystal composition of the present invention.

(c) A comparative liquid crystal composition.

(d) another comparative liquid crystal.

DESCRIPTION OF PREFERRED EMBODIMENTS

The liquid crystalline compound of the present invention expressed bythe formula (1) has a large Δε, a small change in the threshold voltagedepending upon temperatures and a good solubility in other liquidcrystal compositions even at low temperatures. Further, these liquidcrystalline compounds are physically and chemically sufficiently stableunder conditions where display elements are usually used, and further,when the six-membered ring, substituent and/or bonding group, among themolecule-constituting elements are suitably selected, it is possible toderive them into those having desired physical properties. Thus, whenthe compound of the present invention is used as a component of liquidcrystal composition, it is possible to provide a novel liquid crystalcomposition having preferred characteristics.

The compound of the present invention expressed by the formula (1) isclassified into those expressed by the following formulas (1a) to (1l):

Compound having 2 six-membered rings:

    Rg--A.sub.1 --COO--Q                                       (1a)

Compounds having 3 six-membered rings:

    Rg--A.sub.1 --A.sub.2 --COO--Q                             (1b)

    Rg--A.sub.1 --COO--A.sub.2 --Q                             (1c)

    Rg--A.sub.1 --(CH.sub.2).sub.2 --A.sub.2 --COO--Q          (1d)

    Rg--A.sub.1 --COO--A.sub.2 --COO--Q                        (1e)

Compounds having 4 six-membered rings:

    Rg--A.sub.1 --COO--A.sub.2 --A.sub.3 --Q                   (1f)

    Rg--A.sub.1 --A.sub.2 --COO--A.sub.3 --Q                   (1g)

    Rg--A.sub.1 --A.sub.2 --A.sub.3 --COO--Q                   (1h)

    Rg--A.sub.1 --COO--A.sub.2 --COO--A.sub.3 --Q              (1i)

    Rg--A.sub.1 --(CH.sub.2).sub.2 --A.sub.2 --COO--A.sub.3 --Q(1j)

    Rg--A.sub.1 --(CH.sub.2).sub.2 --A.sub.2 --A.sub.3 --COO--Q(1k)

    Rg--A.sub.1 --A.sub.2 --(CH.sub.2).sub.2 --A.sub.3 --COO--Q(1l)

In these formulas, Rg is a group expressed below: ##STR6##

Q is a group expressed below: ##STR7##

The compounds expressed by the formula (1a) are further developed intothe following formulas (1aa) to (1ae):

    Rg--Cyc--COO--Q                                            (1aa)

    Rg--Phe--COO--Q                                            (1ab)

    Rg--Pyr--COO--Q                                            (1ac)

    Rg--Pyd--COO--Q                                            (1ad)

    Rg--Dio--COO--Q                                            (1ae)

Among these compounds, those expressed by (1aa) and (ab) areparticularly preferred.

In the above formulas, Cyc represents trans-1,4-cyclohexylene group; Pherepresents 1,4-phenylene group; Pyr represents pyrimidine-2,5-diylgroup; Pyd represents pyridine-2,5-diyl group; Dio represents1,3-dioxane-2,5-diyl group; one or more hydrogen atoms of the Phe may bereplaced by F; A₁, A₂ and A₃ are selected from the group consisting ofCyc, Phe, Pyr, Pyd and Dio, and preferably two or more Pyr, Pyd, Dio arenot contained in the molecule.

Compounds expressed by the formula (1b) are developed into thoseexpressed by the following formulas (1ba) to (1bj):

    Rg--Cyc--Cyc--COO--Q                                       (1ba)

    Rg--Cyc--Phe--COO--Q                                       (1bb)

    Rg--Phe--Cyc--COO--Q                                       (1bc)

    Rg--Phe--Phe--COO--Q                                       (1bd)

    Rg--Pyr--Phe--COO--Q                                       (1be)

    Rg--Pyr--Cyc--COO--Q                                       (1bf)

    Rg--Pyd--Phe--COO--Q                                       (1bg)

    Rg--Pyd--Cyc--COO--Q                                       (1bh)

    Rg--Dio--Phe--COO--Q                                       (1bi)

    Rg--Dio--Cyc--COO--Q                                       (1bj)

Among these compounds, those expressed by the formulas (1ba) to (1be),(1bg) and (1bi) are particularly preferred.

The compounds expressed by the formula (1c) are further developed intothose expressed by the following formulas (1ca) to (1cn):

    Rg--Cyc--COO--Cyc--Q                                       (1ca)

    Rg--Cyc--COO--Phe--Q                                       (1cb)

    Rg--Cyc--COO--Pyr--Q                                       (1cc)

    Rg--Cyc--COO--Pyd--Q                                       (1cd)

    Rg--Phe--COO--Cyc--Q                                       (1ce)

    Rg--Phe--COO--Phe--Q                                       (1cf)

    Rg--Phe--COO--Pyr--Q                                       (1cg)

    Rg--Phe--COO--Pyd--Q                                       (1ch)

    Rg--Pyr--COO--Phe--Q                                       (1ci)

    Rg--Pyr--COO--Cyc--Q                                       (1cj)

    Rg--Pyd--COO--Phe--Q                                       (1ck)

    Rg--Pyd--COO--Cyc--Q                                       (1cl)

    Rg--Dio--COO--Phe--Q                                       (1cm)

    Rg--Dio--COO--Cyc--Q                                       (1cn)

Among these compounds, those expressed by the formulas (1ca), (1cb),(1ce) and (1cf) are particularly preferred.

The compounds expressed by the formula (1d) are further developed intothose expressed by the following formulas (1da) to (1dk):

    Rg--Cyc--(CH.sub.2).sub.2 Cyc--COO--Q                      (1da)

    Rg--Cyc--(CH.sub.2).sub.2 Phe--COO--Q                      (1db)

    Rg--Phe--(CH.sub.2).sub.2 Cyc--COO--Q                      (1dc)

    Rg--Phe--(CH.sub.2).sub.2 Phe--COO--Q                      (1dd)

    Rg--Phe--(CH.sub.2).sub.2 Pyr--COO--Q                      (1de)

    Rg--Pyr--(CH.sub.2).sub.2 Phe--COO--Q                      (1df)

    Rg--Pyr--(CH.sub.2).sub.2 Cyc--COO--Q                      (1dg)

    Rg--Pyd--(CH.sub.2).sub.2 Phe--COO--Q                      (1dh)

    Rg--Pyd--(CH.sub.2).sub.2 Cyc--COO--Q                      (1di)

    Rg--Dio--(CH.sub.2).sub.2 Phe--COO--Q                      (1dj)

    Rg--Dio--(CH.sub.2).sub.2 Cyc--COO--Q                      (1dk)

Among these compounds, compounds expressed by the formulas (1da) to(1dd) are particularly preferred.

The compounds expressed by the formula (1e) are further developed intocompounds expressed by the following formulas (1ea) to (1ek):

    Rg--Cyc--COO Cyc--COO--Q                                   (1ea)

    Rg--Cyc--COO Phe--COO--Q                                   (1eb)

    Rg--Phe--COO Cyc--COO--Q                                   (1ec)

    Rg--Phe--COO Phe--COO--Q                                   (1ed)

    Rg--Phe--COO Pyr--COO--Q                                   (1ee)

    Rg--Pyr--COO Phe--COO--Q                                   (1ef)

    Rg--Pyr--COO--Cyc--COO--Q                                  (1eg)

    Rg--Pyd--COO--Phe--COO--Q                                  (1eh)

    Rg--Pyd--COO--Cyc--COO--Q                                  (1ei)

    Rg--Dio--COO--Phe--COO--Q                                  (1ej)

    Rg--Dio--COO--Cyc--COO--Q                                  (1ek)

Among these compounds, compounds expressed by the formulas (1ea) to(1ed) are particularly preferred.

The compounds expressed by the formula (1f) are further developed intocompounds expressed by the following formulas (1fa) to (1fh):

    Rg--Cyc--COO--Cyc--Cyc--Q                                  (1fa)

    Rg--Cyc--COO--Cyc--Phe--Q                                  (1fb)

    Rg--Cyc--COO--Phe--Phe--Q                                  (1fc)

    Rg--Cyc--COO--Phe--Cyc--Q                                  (1fd)

    Rg--Phe--COO--Cyc--Cyc--Q                                  (1fe)

    Rg--Phe--COO--Cyc--Phe--Q                                  (1ff)

    Rg--Phe--COO--Phe--Cyc--Q                                  (1fg)

    Rg--Phe--COO--Phe--Phe--Q                                  (1fh)

Among these compounds, compounds expressed by the formulas (1fb), (1fc),(1ff) and (1fh) are particularly preferred.

The compounds expressed by the formula (1g) are further developed intocompounds expressed by the following formulas (1ga) to (1gh):

    Rg--Cyc--Cyc--COO--Cyc--Q                                  (1ga)

    Rg--Cyc--Cyc--COO--Phe--Q                                  (1gb)

    Rg--Cyc--Phe--COO--Cyc--Q                                  (1gc)

    Rg--Cyc--Phe--COO--Phe--Q                                  (1gd)

    Rg--Phe--Cyc--COO--Cyc--Q                                  (1ge)

    Rg--Phe--Cyc--COO--Phe--Q                                  (1gf)

    Rg--Phe--Phe--COO--Cyc--Q                                  (1gg)

    Rg--Phe--Phe--COO--Phe--Q                                  (1gh)

Among these compounds, those expressed by the formulas (1gb), (1gc) and(1gd) are particularly preferred.

The compounds expressed by the formula (1h) are further developed intocompounds expressed by the following formulas (1ha) to (1hh):

    Rg--Cyc--Cyc--Cyc--COO--Q                                  (1ha)

    Rg--Cyc--Cyc--Phe--COO--Q                                  (1hb)

    Rg--Cyc--Phe--Phe--COO--Q                                  (1hc)

    Rg--Cyc--Phe--Cyc--COO--Q                                  (1hd)

    Rg--Phe--Cyc--Cyc--COO--Q                                  (1he)

    Rg--Phe--Phe--Cyc--COO--Q                                  (1hf)

    Rg--Phe--Cyc--Phe--COO--Q                                  (1hg)

    Rg--Phe--Phe--Phe--COO--Q                                  (1hh)

In all of the above mentioned compounds, R₉ represents an alkoxyalkylgroup of 2 to 19 carbon atoms, and particularly preferred groups amongthem are methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl,methoxypentyl, methoxynonyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,ethoxybutyl, propoxymethyl, propoxyethyl, propoxypropyl, butoxymethyl,butoxyethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl anddecyloxymethyl.

As described above, compounds expressed by the formulas, (1aa), (1ab),(1ba), (1bb), (1bc), (1bd), (1be), (1bg), (1bi), (1ca), (1cb), (1ce),(1cf), (1da), (1db), (1dc), (1dd), (1ea), (1eb), (1ec), (1ed), (1fb),(1fc), (1ff), (1fh), (1gb), (1gc), (1gd) and (1hb) can be said to beparticularly preferred, but among them as more preferred compounds,compounds expressed by the following formulas (1-1) to (1-24) can bementioned: ##STR8##

The liquid crystalline compound of the present invention expressed bythe formula (1) can be prepared according to known, general organicsynthesis process. For example, it can be conveniently preparedaccording to the following process: ##STR9##

Namely, it is possible to prepare the compound of the formula (1), byesterification such as dehydration condensation.

In more details, a carboxylic acid derivative (1) is converted into anacid halide (2), by means of a halogenating reagent such as thionylchloride etc., in a solvent such as toluene, benzene, etc. or in theabsence of solvent, followed by reacting (2) with a phenol derivative(3) in a solvent such as toluene, benzene, etc., to obtain the objectivecompound example (4). The reactions in a series is preferably carriedout at a temperature between room temperature and the boiling point ofsolvent, and further in the presence of a base such as pyridine,triethylamine, dimethylaniline, tetramethyl urea, etc. (E. J. Corey etal, Journal of Organic Chemistry, 38, 3223 (1973), C. Raha, OrganicSynthesis, IV, 263 (1963), B. Iselin et al, Helvetica Chimica Acta, 40,373 (1957), M. S. Newman et al, Tetrahedron Letters, 3267 (1967)).

Alternatively, when a carboxylic acid derivative (1) is reacted with aphenol derivative (3), in a solvent such as dichloromethane, chloroform,etc., and in the presence of dicyclohexylcarbodiimide (hereinafterabbreviated to DCC) and dimethylaminopyrimidine (hereinafter abbreviatedto DMAP), it is also possible to obtain the objective compound example(4) (B. Neises et al, Organic Synthesis, 63, 183 (1985)).

The carboxylic acid derivative (1) as one of the raw materials can beprepared for example according to the following process: ##STR10##

Namely, when compound (5) is reacted with a sodium alkoxide, to obtain acompound (6), followed by hydrolysis in the presence of a base such asNaOH, KOH, etc., it is possible to obtain a carboxylic acid derivativeexample (7).

Further, when a Grignard reagent (8), of a dihalogenobenzene isprepared, followed by reacting it with ethylene oxide, to obtain analcohol (9) and then an ether (10), preparing a Grignard reagent of theether and reacting it with CO₂, it is possible to obtain a carboxylicacid derivative example (11).

In the case of the alcohol (9), compounds having an l of 3 or more canbe obtained by reacting with the corresponding ring-form ether in placeof ethylene oxide. Alternatively, (9) can be easily obtained by carryingout carbon number-increasing reaction according to a known, generalorganic synthesis process, for example, to prepare the correspondingderivative of carboxylic acid, aldehyde, ester, etc., followed byreducing the derivative with a reducing agent such as sodium boronhydride (SBH), borane, lithium aluminum hydride (LAH), sodiumbis(2-methoxyethoxy) aluminum hydride (SBMEA, Red-Al) or the like.

Alternatively, it is possible to obtain the carboxylic acid derivativeexample (16), by reducing aldehyde (12) with a reducing agent such asSBH, LAH, diisobutylaluminum hydride (DIBAL) or the like, to obtainalcohol (13), followed by reacting it with a halogenating agent such asthionyl chloride or the like, to obtain halide (14), reacting the halidewith a sodium alkoxide to obtain ether (15) and reacting it with oxalylchloride, to obtain an acid chloride; and hydrolyzing it to obtain acarboxylic derivative example (16).

Among the raw materials, the phenol derivative can be prepared forexample according to the following processes: ##STR11##

Namely, a substituted phenol (17), is converted into an ether substance(18) by means of tetrahydropyranyl group or the like, followed byreacting it with an organolithium reagent such as butyllithium or thelike and iodine, to obtain an iodine substance (19), cyanogenating it,and deprotecting, to obtain a phenol derivative example (20).

Further, the above iodine derivative (19) is reacted with sodiumtrifluoroacetate/copper iodide (G. E. Carr et al, Journal of theChemical Society Parkin Trans, Reactions I, 921 (1988)), or methylfluorosulfonyldifluoroacetate/copper iodine (Q. Y. Chen et al, Journalof the Chemical Society, Chemical Communications, 705 (1989), to obtaina trifluoromethyl substance (21), followed by deprotecting it, to obtaina phenol derivative example (22).

Further, the above ether substance (18) is reacted with an organolithiumreagent such as butyllithium or the like and formylpiperidine, to obtainan aldehyde substance (23), followed by reacting it with a fluorinatingagent such as diethylaminosulfurtrifluoride (DAST) (W. J. Middleton etal, Journal of the Organic Chemistry, 40, 574 (1975), S. Rozen et al,Tetrahedron Letters, 41, 111 (1985), M. Hudlicky, Organic Reactions, 35,513 (1988), P. A. Messina et al, Journal of Fluorine Chemistry, 42, 137(1989)), to obtain a compound (24), and deprotecting it, to obtain aphenol derivative example (25).

Further, the above aldehyde substance (23) is reduced with a reducingagent such as sodium boron hydride (SBH), lithium aluminum hydride,diisobutylaluminum hydride, or bis(2-methoxyethoxy aluminum sodiumhydride or the like, followed by reacting with a fluorinating agent suchas DAST or the like, to obtain a compound (26), and deprotecting it, toobtain a phenol derivative example (27).

Further, another substituted phenol substance (28) is treated in thepresence of nitric acid and sulfuric acid to obtain a nitro compound(29), followed by converting it into a xanthate according to Albert etal's method (Synthetic Communications, 19, 547-552, 1989), fluorinatingit according to Kuroboshi et al's method (Tetrahedron Letters, 33, 29,4173-4176, 1992), catalytically hydrogenating in the presence of Ptcatalyst, to obtain a compound (30), reacting it with hydrochloric acidand sodium nitrite, and hydrolyzing the resulting diazonium salt, toobtain a phenol derivative example (33).

Further, the above nitro compound (29) is reacted in a system ofchlorodifluoromethane/sodium hydroxide (Japanese patent application HyoNo. Hei 4-501575), for fluorination, followed by catalyticallyhydrogenating in the presence of Pt catalyst, to obtain a compound (32),reacting it with hydrochloric acid and sodium nitrite, and hydrolyzingthe resulting diazonium salt, to obtain a phenol derivative example(33).

Either of the thus obtained liquid crystalline compound of the presentinvention exhibit a large Δε, and have a small change in the thresholdvoltage depending on temperatures, are easily blended with variousliquid crystal materials, and have a good solubility therewith even atlow temperatures; hence the compound is far superior as a constitutingcomponent of nematic liquid crystal compositions.

The compound of the present invention is usable as a constitutingcomponent in either of liquid crystal compositions of TFT mode, TN modeand STN mode which at present constituted main current, and compounds ofX═CN in the formula (I) are particularly preferred for STN, andcompounds having X replaced by fluorine are particularly preferred forTFT.

When the compound of the present invention is used as a constitutingcomponent of nematic liquid crystal compositions, compounds having astructure of two rings exhibit a relatively low liquid crystaltemperature range and a low viscosity, and compounds having a structureof 3 or 4 rings exhibit a broad liquid crystal temperature range and arelatively high viscosity; hence when these compounds are adequatelyselected, it is possible to obtain liquid crystal compositions havingdesired physical properties.

Further, the compounds among those of the present invention having a4-substituted phenyl group, a 3-fluoro-4-substituted phenyl group or3,5-difluoro-4-substituted phenyl group exhibit a large Δε, and whenhydrogen atoms in other ring structure are replaced by fluorine atoms,it is possible to impart a further large Δε.

The liquid crystal composition provided by the present invention may becomposed only of a first component containing at least one member of theliquid crystalline compound expressed by the formula (1), but thecomposition is preferred to blend therewith, at least one member ofcompounds selected from the group consisting of those expressed by theabove formulas (2), (3) and (4) (hereinafter abbreviated to the second Acomponent), and/or at least one member of compounds selected from thegroup consisting of those expressed by the formulas (5), (6), (7), (8)and (9) (hereinafter abbreviated to the second B component), andfurther, it is possible to additionally blend known compounds as thethird component, in order to adjust the threshold voltage, liquidcrystal phase temperature range, optical anisotropy value, dielectricanisotropy value, viscosity, etc.

As preferred examples of compounds contained in those expressed by theformulas (2), (3) and (4), among the second A component, the followingcompounds of (2-1) to (2-15), (3-1) to (3-48) and (4-1) to (4-55) can berespectively mentioned: ##STR12##

The compounds expressed by these formulas (2) to (4) exhibit a positivedielectric anisotropy value and far superior thermal stability andchemical stability.

As to the quantity of the compounds used, a range of 1 to 99% by weightbased upon the total weight is suitable, and that of 10 to 97% by weightis preferred, and that of 40 to 95% by weight is more preferred.

Next, as preferred examples of the compounds expressed by the formulas(5), (6) and (7), among the above second B component, the following(5-1) to (5-29), (6-1) to (6-3) and (7-1) to (7-17) can be mentioned:##STR13##

The compounds expressed by the formulas (5) to (7) exhibit a positiveand large dielectric anisotropy value and are used as compositioncomponent, particularly in order to reduce the threshold voltage.Further, the compounds are used for adjusting the viscosity and theoptical anisotropy value and for broadening the liquid crystal phasetemperature range, and further for improving the steepness.

Further, as preferable examples of compounds included in those of theformulas (8) and (9), among those of the second B component, thefollowing (8-1) to (8-16) and (9-1) to (9-16) can be mentioned:##STR14##

The compounds expressed by the formulas (8) and (9) exhibit a negativeor weakly positive dielectric anisotropy value, and among thesecompounds, those expressed by the formula (8) are used as a compositioncomponent, mainly for lowering the viscosity and adjusting the opticalanisotropy value, and those expressed by the formula (9) are used forbroadening the liquid crystal phase temperature range and/or foradjusting the optical anisotropy value.

The compounds expressed by the formulas (5) to (9) are indispensable forpreparing liquid crystal compositions, particularly for STN type displaymode or usual TN type display mode. As to the quantity of thesecompounds used, when liquid crystal compositions for usual STN typedisplay mode or TN type display mode are prepared, a range of 1 to 99%by weight based upon the total quantity of the liquid crystalcompositions is suitable, and a range of 10 to 97% is preferred and thatof 40 to 95% by weight is more preferred.

The liquid crystal composition provided by the present invention ispreferred to contain at least one member of the liquid crystal compoundexpressed by the formula (1) in a proportion of 0.1 to 99% by weight,for exhibiting superior characteristics.

The liquid crystal composition is generally prepared according to aknown process, for example according to a process wherein variouscomponents are mutually dissolved at high temperatures. Further, ifnecessary, by adding a suitable additive, improvement is made dependingupon the aimed use applications and the composition is optimized. Suchadditives are well known by preson of ordinary skill in the art anddescribed in literatures, etc. in details. Usually, a chiral dopanthaving an effect of inducing the helical structure to thereby adjust anecessary twist angle and prevent the reverse twist, is added.

Further, when a dichroic pigment such as those of mellocyanine group,styryl group, azo group, azomethine group, azoxy group, quinophthalonegroup, anthraquinone group, tetrazine group, etc. is added, theresulting composition can be also used as that of GH mode. Thecomposition of the present invention is usable for NCAP prepared bymicrocapsulating nematic liquid crystals, polymer-dispersion type,liquid crystal display element prepared by forming three-dimensional,reticulated high molecules in liquid crystals (PDLCD), for example,polymer network liquid crystal display element (PNLCD) and besides, asliquid crystal compositions for birefringence control (ECB) mode or DSmode.

As liquid crystal composition examples containing the compound of thepresent invention, the following ones can be mentioned:

In addition, the numbers of the compounds are the same as those shown inthe below-mentioned Examples.

    __________________________________________________________________________    Composition example 1                                                          ##STR15##                                  4 wt. %                            ##STR16##                                  4 wt. %                            ##STR17##                                  4 wt. %                            ##STR18##                                  6 wt. %                            ##STR19##                                  6 wt. %                            ##STR20##                                  6 wt. %                            ##STR21##                                  5 wt. %                            ##STR22##                                  5 wt. %                            ##STR23##                                  4 wt. %                            ##STR24##                                  12 wt. %                           ##STR25##                                  10 wt. %                           ##STR26##                                  6 wt. %                            ##STR27##                                  5 wt. %                            ##STR28##                                  5 wt. %                            ##STR29##                                  10 wt. %                           ##STR30##                                  8 wt. %                           Composition example 2                                                          ##STR31##                                  5 wt. %                            ##STR32##                                  5 wt. %                            ##STR33##                                  5 wt. %                            ##STR34##                                  5 wt. %                            ##STR35##                                  5 wt. %                            ##STR36##                                  5 wt. %                            ##STR37##                                  10 wt. %                           ##STR38##                                  12 wt. %                           ##STR39##                                  11 wt. %                           ##STR40##                                  8 wt. %                            ##STR41##                                  4 wt. %                            ##STR42##                                  4 wt. %                            ##STR43##                                  3 wt. %                            ##STR44##                                  3 wt. %                            ##STR45##                                  3 wt. %                            ##STR46##                                  4 wt. %                            ##STR47##                                  4 wt. %                            ##STR48##                                  4 wt. %                           Composition example 3                                                          ##STR49##                                  10 wt. %                           ##STR50##                                  5 wt. %                            ##STR51##                                  8 wt. %                            ##STR52##                                  10 wt. %                           ##STR53##                                  15 wt. %                           ##STR54##                                  8 wt. %                            ##STR55##                                  5 wt. %                            ##STR56##                                  5 wt. %                            ##STR57##                                  4 wt. %                            ##STR58##                                  6 wt. %                            ##STR59##                                  6 wt. %                            ##STR60##                                  3 wt. %                            ##STR61##                                  3 wt. %                            ##STR62##                                  4 wt. %                            ##STR63##                                  4 wt. %                            ##STR64##                                  4 wt. %                           Composition example 4                                                          ##STR65##                                  6 wt. %                            ##STR66##                                  5 wt. %                            ##STR67##                                  5 wt. %                            ##STR68##                                  3 wt. %                            ##STR69##                                  6 wt. %                            ##STR70##                                  4 wt. %                            ##STR71##                                  4 wt. %                            ##STR72##                                  4 wt. %                            ##STR73##                                  5 wt. %                            ##STR74##                                  5 wt. %                            ##STR75##                                  5 wt. %                            ##STR76##                                  5 wt. %                            ##STR77##                                  5 wt. %                            ##STR78##                                  5 wt. %                            ##STR79##                                  6 wt. %                            ##STR80##                                  4 wt. %                            ##STR81##                                  4 wt. %                            ##STR82##                                  5 wt. %                            ##STR83##                                  5 wt. %                            ##STR84##                                  3 wt. %                            ##STR85##                                  3 wt. %                            ##STR86##                                  3 wt. %                           Composition example 5                                                          ##STR87##                                  8 wt. %                            ##STR88##                                  5 wt. %                            ##STR89##                                  5 wt. %                            ##STR90##                                  5 wt. %                            ##STR91##                                  8 wt. %                            ##STR92##                                  4 wt. %                            ##STR93##                                  10 wt. %                           ##STR94##                                  3 wt. %                            ##STR95##                                  4 wt. %                            ##STR96##                                  3 wt. %                            ##STR97##                                  6 wt. %                            ##STR98##                                  6 wt. %                            ##STR99##                                  4 wt. %                            ##STR100##                                 5 wt. %                            ##STR101##                                 5 wt. %                            ##STR102##                                 5 wt. %                            ##STR103##                                 6 wt. %                            ##STR104##                                 4 wt. %                            ##STR105##                                 4 wt. %                           Composition example 6                                                          ##STR106##                                 6 wt. %                            ##STR107##                                 6 wt. %                            ##STR108##                                 5 wt. %                            ##STR109##                                 8 wt. %                            ##STR110##                                 10 wt. %                           ##STR111##                                 8 wt. %                            ##STR112##                                 3 wt. %                            ##STR113##                                 3 wt. %                            ##STR114##                                 4 wt. %                            ##STR115##                                 5 wt. %                            ##STR116##                                 3 wt. %                            ##STR117##                                 3 wt. %                            ##STR118##                                 3 wt. %                            ##STR119##                                 3 wt. %                            ##STR120##                                 5 wt. %                            ##STR121##                                 6 wt. %                            ##STR122##                                 5 wt. %                            ##STR123##                                 4 wt. %                            ##STR124##                                 4 wt. %                            ##STR125##                                 6 wt. %                           Composition example 7                                                          ##STR126##                                 6 wt. %                            ##STR127##                                 6 wt. %                            ##STR128##                                 4 wt. %                            ##STR129##                                 4 wt. %                            ##STR130##                                 10 wt. %                           ##STR131##                                 10 wt. %                           ##STR132##                                 5 wt. %                            ##STR133##                                 5 wt. %                            ##STR134##                                 6 wt. %                            ##STR135##                                 4 wt. %                            ##STR136##                                 5 wt. %                            ##STR137##                                 3 wt. %                            ##STR138##                                 3 wt. %                            ##STR139##                                 10 wt. %                           ##STR140##                                 4 wt. %                            ##STR141##                                 3 wt. %                            ##STR142##                                 6 wt. %                            ##STR143##                                 3 wt. %                            ##STR144##                                 3 wt. %                           Composition example 8                                                          ##STR145##                                 10 wt. %                           ##STR146##                                 9 wt. %                            ##STR147##                                 5 wt. %                            ##STR148##                                 5 wt. %                            ##STR149##                                 15 wt. %                           ##STR150##                                 5 wt. %                            ##STR151##                                 5 wt. %                            ##STR152##                                 5 wt. %                            ##STR153##                                 10 wt. %                           ##STR154##                                 8 wt. %                            ##STR155##                                 3 wt. %                            ##STR156##                                 4 wt. %                            ##STR157##                                 4 wt. %                            ##STR158##                                 4 wt. %                            ##STR159##                                 5 wt. %                            ##STR160##                                 3 wt. %                           Composition example 9                                                          ##STR161##                                 6 wt. %                            ##STR162##                                 6 wt. %                            ##STR163##                                 3 wt. %                            ##STR164##                                 3 wt. %                            ##STR165##                                 8 wt. %                            ##STR166##                                 8 wt. %                            ##STR167##                                 15 wt. %                           ##STR168##                                 8 wt. %                            ##STR169##                                 4 wt. %                            ##STR170##                                 4 wt. %                            ##STR171##                                 2 wt. %                            ##STR172##                                 2 wt. %                            ##STR173##                                 6 wt. %                            ##STR174##                                 6 wt. %                            ##STR175##                                 3 wt. %                            ##STR176##                                 5 wt. %                            ##STR177##                                 8 wt. %                            ##STR178##                                 3 wt. %                           Composition example 10                                                         ##STR179##                                 6 wt. %                            ##STR180##                                 5 wt. %                            ##STR181##                                 6 wt. %                            ##STR182##                                 3 wt. %                            ##STR183##                                 3 wt. %                            ##STR184##                                 4 wt. %                            ##STR185##                                 10 wt. %                           ##STR186##                                 10 wt. %                           ##STR187##                                 10 wt. %                           ##STR188##                                 4 wt. %                            ##STR189##                                 2 wt. %                            ##STR190##                                 4 wt. %                            ##STR191##                                 4 wt. %                            ##STR192##                                 4 wt. %                            ##STR193##                                 8 wt. %                            ##STR194##                                 3 wt. %                            ##STR195##                                 3 wt. %                            ##STR196##                                 2 wt. %                            ##STR197##                                 4 wt. %                            ##STR198##                                 5 wt. %                           Composition example 11                                                         ##STR199##                                 5 wt. %                            ##STR200##                                 5 wt. %                            ##STR201##                                 5 wt. %                            ##STR202##                                 4 wt. %                            ##STR203##                                 4 wt. %                            ##STR204##                                 5 wt. %                            ##STR205##                                 6 wt. %                            ##STR206##                                 5 wt. %                            ##STR207##                                 4 wt. %                            ##STR208##                                 6 wt. %                            ##STR209##                                 6 wt. %                            ##STR210##                                 12 wt. %                           ##STR211##                                 13 wt. %                           ##STR212##                                 13 wt. %                           ##STR213##                                 3 wt. %                            ##STR214##                                 4 wt. %                           Composition example 12                                                         ##STR215##                                 8 wt. %                            ##STR216##                                 6 wt. %                            ##STR217##                                 6 wt. %                            ##STR218##                                 7 wt. %                            ##STR219##                                 8 wt. %                            ##STR220##                                 8 wt. %                            ##STR221##                                 8 wt. %                            ##STR222##                                 6 wt. %                            ##STR223##                                 3 wt. %                            ##STR224##                                 6 wt. %                            ##STR225##                                 3 wt. %                            ##STR226##                                 3 wt. %                            ##STR227##                                 4 wt. %                            ##STR228##                                 3 wt. %                            ##STR229##                                 5 wt. %                            ##STR230##                                 3 wt. %                            ##STR231##                                 3 wt. %                            ##STR232##                                 3 wt. %                            ##STR233##                                 3 wt. %                            ##STR234##                                 4 wt. %                           Composition exmaple 13                                                         ##STR235##                                 3 wt. %                            ##STR236##                                 3 wt. %                            ##STR237##                                 5 wt. %                            ##STR238##                                 4 wt. %                            ##STR239##                                 5 wt. %                            ##STR240##                                 11 wt. %                           ##STR241##                                 11 wt. %                           ##STR242##                                 11 wt. %                           ##STR243##                                 5 wt. %                            ##STR244##                                 5 wt. %                            ##STR245##                                 10 wt. %                           ##STR246##                                 3 wt. %                            ##STR247##                                 3 wt. %                            ##STR248##                                 4 wt. %                            ##STR249##                                 4 wt. %                            ##STR250##                                 3 wt. %                            ##STR251##                                 3 wt. %                            ##STR252##                                 2 wt. %                            ##STR253##                                 5 wt. %                           Composition example 14                                                         ##STR254##                                 5 wt. %                            ##STR255##                                 4 wt. %                            ##STR256##                                 4 wt. %                            ##STR257##                                 4 wt. %                            ##STR258##                                 2 wt. %                            ##STR259##                                 7 wt. %                            ##STR260##                                 8 wt. %                            ##STR261##                                 4 wt. %                            ##STR262##                                 10 wt. %                           ##STR263##                                 8 wt. %                            ##STR264##                                 8 wt. %                            ##STR265##                                 12 wt. %                           ##STR266##                                 8 wt. %                            ##STR267##                                 8 wt. %                            ##STR268##                                 8 wt. %                           Composition example 15                                                         ##STR269##                                 8 wt. %                            ##STR270##                                 6 wt. %                            ##STR271##                                 5 wt. %                            ##STR272##                                 2 wt. %                            ##STR273##                                 2 wt. %                            ##STR274##                                 10 wt. %                           ##STR275##                                 8 wt. %                            ##STR276##                                 8 wt. %                            ##STR277##                                 5 wt. %                            ##STR278##                                 5 wt. %                            ##STR279##                                 5 wt. %                            ##STR280##                                 5 wt. %                            ##STR281##                                 4 wt. %                            ##STR282##                                 4 wt. %                            ##STR283##                                 10 wt. %                           ##STR284##                                 8 wt. %                            ##STR285##                                 3 wt. %                            ##STR286##                                 2 wt. %                           Composition example 16                                                         ##STR287##                                 10 wt. %                           ##STR288##                                 6 wt. %                            ##STR289##                                 5 wt. %                            ##STR290##                                 12 wt. %                           ##STR291##                                 12 wt. %                           ##STR292##                                 5 wt. %                            ##STR293##                                 5 wt. %                            ##STR294##                                 5 wt. %                            ##STR295##                                 12 wt. %                           ##STR296##                                 10 wt. %                           ##STR297##                                 5 wt. %                            ##STR298##                                 5 wt. %                            ##STR299##                                 4 wt. %                            ##STR300##                                 4 wt. %                           Composition example 17                                                         ##STR301##                                 5 wt. %                            ##STR302##                                 5 wt. %                            ##STR303##                                 5 wt. %                            ##STR304##                                 5 wt. %                            ##STR305##                                 3 wt. %                            ##STR306##                                 4 wt. %                            ##STR307##                                 3 wt. %                            ##STR308##                                 6 wt. %                            ##STR309##                                 5 wt. %                            ##STR310##                                 6 wt. %                            ##STR311##                                 4 wt. %                            ##STR312##                                 6 wt. %                            ##STR313##                                 5 wt. %                            ##STR314##                                 6 wt. %                            ##STR315##                                 6 wt. %                            ##STR316##                                 4 wt. %                            ##STR317##                                 3 wt. %                            ##STR318##                                 3 wt. %                            ##STR319##                                 3 wt. %                            ##STR320##                                 3 wt. %                            ##STR321##                                 6 wt. %                            ##STR322##                                 4 wt. %                           Composition example 18                                                         ##STR323##                                 8 wt. %                            ##STR324##                                 8 wt. %                            ##STR325##                                 5 wt. %                            ##STR326##                                 5 wt. %                            ##STR327##                                 5 wt. %                            ##STR328##                                 6 wt. %                            ##STR329##                                 6 wt. %                            ##STR330##                                 5 wt. %                            ##STR331##                                 5 wt. %                            ##STR332##                                 4 wt. %                            ##STR333##                                 4 wt. %                            ##STR334##                                 6 wt. %                            ##STR335##                                 6 wt. %                            ##STR336##                                 4 wt. %                            ##STR337##                                 4 wt. %                            ##STR338##                                 5 wt. %                            ##STR339##                                 8 wt. %                            ##STR340##                                 3 wt. %                            ##STR341##                                 3 wt. %                           Composition example 19                                                         ##STR342##                                 12 wt. %                           ##STR343##                                 12 wt. %                           ##STR344##                                 3 wt. %                            ##STR345##                                 10 wt. %                           ##STR346##                                 7 wt. %                            ##STR347##                                 9 wt. %                            ##STR348##                                 6 wt. %                            ##STR349##                                 5 wt. %                            ##STR350##                                 5 wt. %                            ##STR351##                                 9 wt. %                            ##STR352##                                 5 wt. %                            ##STR353##                                 5 wt. %                            ##STR354##                                 5 wt. %                            ##STR355##                                 7 wt. %                           Composition example 20                                                         ##STR356##                                 5 wt. %                            ##STR357##                                 5 wt. %                            ##STR358##                                 5 wt. %                            ##STR359##                                 5 wt. %                            ##STR360##                                 5 wt. %                            ##STR361##                                 5 wt. %                            ##STR362##                                 10 wt. %                           ##STR363##                                 12 wt. %                           ##STR364##                                 11 wt. %                           ##STR365##                                 8 wt. %                            ##STR366##                                 4 wt. %                            ##STR367##                                 4 wt. %                            ##STR368##                                 3 wt. %                            ##STR369##                                 3 wt. %                            ##STR370##                                 3 wt. %                            ##STR371##                                 4 wt. %                            ##STR372##                                 4 wt. %                            ##STR373##                                 4 wt. %                           Composition example 21                                                         ##STR374##                                 6 wt. %                            ##STR375##                                 5 wt. %                            ##STR376##                                 5 wt. %                            ##STR377##                                 3 wt. %                            ##STR378##                                 6 wt. %                            ##STR379##                                 4 wt. %                            ##STR380##                                 4 wt. %                            ##STR381##                                 4 wt. %                            ##STR382##                                 5 wt. %                            ##STR383##                                 5 wt. %                            ##STR384##                                 5 wt. %                            ##STR385##                                 5 wt. %                            ##STR386##                                 5 wt. %                            ##STR387##                                 5 wt. %                            ##STR388##                                 6 wt. %                            ##STR389##                                 4 wt. %                            ##STR390##                                 4 wt. %                            ##STR391##                                 5 wt. %                            ##STR392##                                 5 wt. %                            ##STR393##                                 3 wt. %                            ##STR394##                                 3 wt. %                            ##STR395##                                 3 wt. %                           Composition example 22                                                         ##STR396##                                 6 wt. %                            ##STR397##                                 6 wt. %                            ##STR398##                                 4 wt. %                            ##STR399##                                 4 wt. %                            ##STR400##                                 10 wt. %                           ##STR401##                                 10 wt. %                           ##STR402##                                 5 wt. %                            ##STR403##                                 5 wt. %                            ##STR404##                                 6 wt. %                            ##STR405##                                 4 wt. %                            ##STR406##                                 5 wt. %                            ##STR407##                                 3 wt. %                            ##STR408##                                 3 wt. %                            ##STR409##                                 10 wt. %                           ##STR410##                                 4 wt. %                            ##STR411##                                 3 wt. %                            ##STR412##                                 6 wt. %                            ##STR413##                                 3 wt. %                            ##STR414##                                 3 wt. %                           Composition example 23                                                         ##STR415##                                 10 wt. %                           ##STR416##                                 9 wt. %                            ##STR417##                                 5 wt. %                            ##STR418##                                 5 wt. %                            ##STR419##                                 15 wt. %                           ##STR420##                                 5 wt. %                            ##STR421##                                 5 wt. %                            ##STR422##                                 5 wt. %                            ##STR423##                                 10 wt. %                           ##STR424##                                 8 wt. %                            ##STR425##                                 3 wt. %                            ##STR426##                                 4 wt. %                            ##STR427##                                 4 wt. %                            ##STR428##                                 4 wt. %                            ##STR429##                                 5 wt. %                            ##STR430##                                 3 wt. %                           Composition example 24                                                         ##STR431##                                 5 wt. %                            ##STR432##                                 5 wt. %                            ##STR433##                                 5 wt. %                            ##STR434##                                 4 wt. %                            ##STR435##                                 4 wt. %                            ##STR436##                                 5 wt. %                            ##STR437##                                 6 wt. %                            ##STR438##                                 5 wt. %                            ##STR439##                                 4 wt. %                            ##STR440##                                 6 wt. %                            ##STR441##                                 6 wt. %                            ##STR442##                                 12 wt. %                           ##STR443##                                 13 wt. %                           ##STR444##                                 13 wt. %                           ##STR445##                                 3 wt. %                            ##STR446##                                 4 wt. %                           Composition example 25                                                         ##STR447##                                 3 wt. %                            ##STR448##                                 3 wt. %                            ##STR449##                                 5 wt. %                            ##STR450##                                 4 wt. %                            ##STR451##                                 5 wt. %                            ##STR452##                                 11 wt. %                           ##STR453##                                 11 wt. %                           ##STR454##                                 11 wt. %                           ##STR455##                                 5 wt. %                            ##STR456##                                 5 wt. %                            ##STR457##                                 10 wt. %                           ##STR458##                                 3 wt. %                            ##STR459##                                 3 wt. %                            ##STR460##                                 4 wt. %                            ##STR461##                                 4 wt. %                            ##STR462##                                 3 wt. %                            ##STR463##                                 3 wt. %                            ##STR464##                                 2 wt. %                            ##STR465##                                 5 wt. %                           Composition example 26                                                         ##STR466##                                 10 wt. %                           ##STR467##                                 6 wt. %                            ##STR468##                                 5 wt. %                            ##STR469##                                 12 wt. %                           ##STR470##                                 12 wt. %                           ##STR471##                                 5 wt. %                            ##STR472##                                 5 wt. %                            ##STR473##                                 5 wt. %                            ##STR474##                                 12 wt. %                           ##STR475##                                 10 wt. %                           ##STR476##                                 5 wt. %                            ##STR477##                                 5 wt. %                            ##STR478##                                 4 wt. %                            ##STR479##                                 4 wt. %                           Composition example 27                                                         ##STR480##                                 8 wt. %                            ##STR481##                                 6 wt. %                            ##STR482##                                 5 wt. %                            ##STR483##                                 2 wt. %                            ##STR484##                                 2 wt. %                            ##STR485##                                 10 wt. %                           ##STR486##                                 8 wt. %                            ##STR487##                                 8 wt. %                            ##STR488##                                 5 wt. %                            ##STR489##                                 5 wt. %                            ##STR490##                                 5 wt. %                            ##STR491##                                 5 wt. %                            ##STR492##                                 4 wt. %                            ##STR493##                                 4 wt. %                            ##STR494##                                 10 wt. %                           ##STR495##                                 8 wt. %                            ##STR496##                                 3 wt. %                            ##STR497##                                 2 wt. %                           Composition example 28                                                         ##STR498##                                 8 wt. %                            ##STR499##                                 6 wt. %                            ##STR500##                                 6 wt. %                            ##STR501##                                 7 wt. %                            ##STR502##                                 8 wt. %                            ##STR503##                                 8 wt. %                            ##STR504##                                 8 wt. %                            ##STR505##                                 6 wt. %                            ##STR506##                                 3 wt. %                            ##STR507##                                 6 wt. %                            ##STR508##                                 3 wt. %                            ##STR509##                                 3 wt. %                            ##STR510##                                 4 wt. %                            ##STR511##                                 3 wt. %                            ##STR512##                                 5 wt. %                            ##STR513##                                 3 wt. %                            ##STR514##                                 3 wt. %                            ##STR515##                                 3 wt. %                            ##STR516##                                 3 wt. %                            ##STR517##                                 4 wt. %                           Composition example 29                                                         ##STR518##                                 5 wt. %                            ##STR519##                                 10 wt. %                           ##STR520##                                 5 wt. %                            ##STR521##                                 5 wt. %                            ##STR522##                                 8 wt. %                            ##STR523##                                 7 wt. %                            ##STR524##                                 10 wt. %                           ##STR525##                                 5 wt. %                            ##STR526##                                 10 wt. %                           ##STR527##                                 10 wt. %                           ##STR528##                                 10 wt. %                           ##STR529##                                 8 wt. %                            ##STR530##                                 7 wt. %                           Composition example 30                                                         ##STR531##                                 10 wt. %                           ##STR532##                                 5 wt. %                            ##STR533##                                 11 wt. %                           ##STR534##                                 11 wt. %                           ##STR535##                                 11 wt. %                           ##STR536##                                 5 wt. %                            ##STR537##                                 7 wt. %                            ##STR538##                                 2 wt. %                            ##STR539##                                 2 wt. %                            ##STR540##                                 2 wt. %                            ##STR541##                                 2 wt. %                            ##STR542##                                 2 wt. %                            ##STR543##                                 5 wt. %                            ##STR544##                                 10 wt. %                           ##STR545##                                 3 wt. %                            ##STR546##                                 3 wt. %                            ##STR547##                                 4 wt. %                            ##STR548##                                 5 wt. %                           Composition example 31                                                         ##STR549##                                 10 wt. %                           ##STR550##                                 10 wt. %                           ##STR551##                                 4 wt. %                            ##STR552##                                 10 wt. %                           ##STR553##                                 15 wt. %                           ##STR554##                                 10 wt. %                           ##STR555##                                 10 wt. %                           ##STR556##                                 4 wt. %                            ##STR557##                                 5 wt. %                            ##STR558##                                 5 wt. %                            ##STR559##                                 9 wt. %                            ##STR560##                                 8 wt. %                           Composition example 32                                                         ##STR561##                                 8 wt. %                            ##STR562##                                 10 wt. %                           ##STR563##                                 7 wt. %                            ##STR564##                                 10 wt. %                           ##STR565##                                 5 wt. %                            ##STR566##                                 10 wt. %                           ##STR567##                                 10 wt. %                           ##STR568##                                 3 wt. %                            ##STR569##                                 7 wt. %                            ##STR570##                                 6 wt. %                            ##STR571##                                 6 wt. %                            ##STR572##                                 2 wt. %                            ##STR573##                                 2 wt. %                            ##STR574##                                 2 wt. %                            ##STR575##                                 2 wt. %                            ##STR576##                                 5 wt. %                            ##STR577##                                 5 wt. %                           Composition example 33                                                         ##STR578##                                 5 wt. %                            ##STR579##                                 5 wt. %                            ##STR580##                                 7 wt. %                            ##STR581##                                 7 wt. %                            ##STR582##                                 7 wt. %                            ##STR583##                                 8 wt. %                            ##STR584##                                 6 wt. %                            ##STR585##                                 5 wt. %                            ##STR586##                                 4 wt. %                            ##STR587##                                 7 wt. %                            ##STR588##                                 1.1 wt. %                          ##STR589##                                 2.3 wt. %                          ##STR590##                                 2.1 wt. %                          ##STR591##                                 4.5 wt. %                          ##STR592##                                 2 wt. %                            ##STR593##                                 14 wt. %                           ##STR594##                                 7 wt. %                            ##STR595##                                 3 wt. %                            ##STR596##                                 3 wt. %                           Composition example 34                                                         ##STR597##                                 4 wt. %                            ##STR598##                                 5 wt. %                            ##STR599##                                 5 wt. %                            ##STR600##                                 9 wt. %                            ##STR601##                                 9 wt. %                            ##STR602##                                 8 wt. %                            ##STR603##                                 4 wt. %                            ##STR604##                                 5 wt. %                            ##STR605##                                 8 wt. %                            ##STR606##                                 5 wt. %                            ##STR607##                                 11 wt. %                           ##STR608##                                 5 wt. %                            ##STR609##                                 5 wt. %                            ##STR610##                                 8 wt. %                            ##STR611##                                 7 wt. %                            ##STR612##                                 2 wt. %                           Composition example 35                                                         ##STR613##                                 5 wt. %                            ##STR614##                                 20 wt. %                           ##STR615##                                 10 wt. %                           ##STR616##                                 10 wt. %                           ##STR617##                                 10 wt. %                           ##STR618##                                 5 wt. %                            ##STR619##                                 6 wt. %                            ##STR620##                                 6 wt. %                            ##STR621##                                 6 wt. %                            ##STR622##                                 4 wt. %                            ##STR623##                                 6 wt. %                            ##STR624##                                 6 wt. %                            ##STR625##                                 3 wt. %                            ##STR626##                                 3 wt. %                           Composition example 36                                                         ##STR627##                                 6 wt. %                            ##STR628##                                 10 wt. %                           ##STR629##                                 10 wt. %                           ##STR630##                                 12 wt. %                           ##STR631##                                 4 wt. %                            ##STR632##                                 3 wt. %                            ##STR633##                                 3 wt. %                            ##STR634##                                 3 wt. %                            ##STR635##                                 11 wt. %                           ##STR636##                                 8.3 wt. %                          ##STR637##                                 8.3 wt. %                          ##STR638##                                 6.9 wt. %                          ##STR639##                                 5.5 wt. %                          ##STR640##                                 3 wt. %                            ##STR641##                                 6 wt. %                           Composition example 37                                                         ##STR642##                                 10 wt. %                           ##STR643##                                 5 wt. %                            ##STR644##                                 5 wt. %                            ##STR645##                                 10 wt. %                           ##STR646##                                 10 wt. %                           ##STR647##                                 10 wt. %                           ##STR648##                                 10 wt. %                           ##STR649##                                 5 wt. %                            ##STR650##                                 5 wt. %                            ##STR651##                                 10 wt. %                           ##STR652##                                 10 wt. %                           ##STR653##                                 10 wt. %                          Composition example 38                                                         ##STR654##                                 10 wt. %                           ##STR655##                                 5 wt. %                            ##STR656##                                 15 wt. %                           ##STR657##                                 5 wt. %                            ##STR658##                                 10 wt. %                           ##STR659##                                 11 wt. %                           ##STR660##                                 11 wt. %                           ##STR661##                                 9 wt. %                            ##STR662##                                 4 wt. %                            ##STR663##                                 4 wt. %                            ##STR664##                                 4 wt. %                            ##STR665##                                 6 wt. %                            ##STR666##                                 6 wt. %                           Composition example 39                                                         ##STR667##                                 10 wt. %                           ##STR668##                                 12 wt. %                           ##STR669##                                 3 wt. %                            ##STR670##                                 7 wt. %                            ##STR671##                                 10 wt. %                           ##STR672##                                 5 wt. %                            ##STR673##                                 5 wt. %                            ##STR674##                                 9 wt. %                            ##STR675##                                 9 wt. %                            ##STR676##                                 8 wt. %                            ##STR677##                                 5 wt. %                            ##STR678##                                 5 wt. %                            ##STR679##                                 5 wt. %                            ##STR680##                                 7 wt. %                           Composition example 40                                                         ##STR681##                                 12 wt. %                           ##STR682##                                 12 wt. %                           ##STR683##                                 3 wt. %                            ##STR684##                                 10 wt. %                           ##STR685##                                 7 wt. %                            ##STR686##                                 5 wt. %                            ##STR687##                                 5 wt. %                            ##STR688##                                 9 wt. %                            ##STR689##                                 6 wt. %                            ##STR690##                                 9 wt. %                            ##STR691##                                 5 wt. %                            ##STR692##                                 5 wt. %                            ##STR693##                                 5 wt. %                            ##STR694##                                 7 wt. %                           __________________________________________________________________________

EXAMPLE

The present invention will be described in more details by way ofExamples. In addition, in the respective Examples, Cr, S_(A), S_(B), Sc,S_(X), N and Iso, respectively represent crystal, smectic A phase,smectic B phase, smectic C phase, smectic phase whose phase structurehas not yet been analyzed, nematic phase, and isotropic liquid. The unitof the phase transition temperatures all refer to °C.

Example 1

Preparation of 3,5-difluoro-4-cyanophenyl 4-(pentyloxymethyl)benzoate(in the formula (1), R=C₅ H₁₁, l=1, m=1, n and o=both, 0; A₁ =1,4-phenylene group, Z₁ =--COO--, X=CN, and Y₁ and Y₂ =both, F) (CompoundNo. 1)) 4-(Pentyloxymethyl)benzoic acid. (1.6 g, 7.1 mmol) was mixedwith thionyl chloride (1.3 g, 10.6 mmol), pyridine (0.1 ml) and toluene(3 ml), followed by reacting them at 80° C. for 2 hours, and distillingoff superfluous thionyl chloride and toluene under reduced pressure, toobtain raw 4-(pentyloxymethyl)benzoyl chloride.

Next, 2,6-difluoro-4-hydroxybenzonitrile (1.1 g, 7.1 mmol), pyridine(0.8 ml) and toluene (2 ml) were mixed. To this mixture was dropwiseadded a toluene 3 ml solution of the above 4-(pentyloxymethyl)benzoylchloride, at room temperature for 10 minutes, followed by reacting themat 50° C. for 2 hours, addign water (10 ml) to the reaction product,extracting with toluene (50 ml), washing the resulting organic layerthree times with 6N-HCl, three times with 2N-NaOH and three times withwater, drying over anhydrous magnesium sulfate, distilling off thesolvent under reduced pressure, subjecting the residue to silica gelcolumn chromatography (eluent: toluene), to obtain raw3,5-difluoro-4-cyanophenyl 4- (pentyloxymethyl)benzoate (2.5 g), andrecrystallizing this product from heptane/ether (6/4), to obtain thecaptioned compound (1.8 g) (yield: 69.0%).

Cr 32.6˜33.3 Iso

Further, the mass spector data well supported its structure.

Mass analysis: 360 (M+1).

According to the process of Example 1, the following compounds (No. 2 toNo. 42) are prepared.

In addition, the respective compounds were represented by extracting R,l, A=--(A₁ --Z₁)_(m) --(A₂ --Z₂)_(n) --(A₃ --Z₃)_(o) --, X, Y₁ and Y₂ asparameters in the compounds expressed by the formula (1).

(This applies to the succeeding Examples.)

    __________________________________________________________________________    No.                                                                              R    1 A           X     Y.sub.1                                                                         Y.sub.2                                         __________________________________________________________________________    2  CH.sub.3                                                                           1                                                                                ##STR695## CN    F F                                               3  C.sub.2 H.sub.5                                                                    1                                                                                ##STR696## CN    F F                                               4  C.sub.3 H.sub.7                                                                    1                                                                                ##STR697## CN    F F Cr room temp. or lower Iso                    5  C.sub.4 H.sub.9                                                                    1                                                                                ##STR698## CN    F F Cr room temp. or lower Iso                    6  CH.sub.3                                                                           1                                                                                ##STR699## CF.sub.3                                                                            F F                                               7  C.sub.2 H.sub.5                                                                    1                                                                                ##STR700## CF.sub.3                                                                            F F                                               8  C.sub.3 H.sub.7                                                                    1                                                                                ##STR701## CF.sub.3                                                                            F F Cr room temp. or lower Iso                    9  C.sub.4 H.sub.9                                                                    1                                                                                ##STR702## CF.sub.3                                                                            F F                                               10 C.sub.5 H.sub.11                                                                   1                                                                                ##STR703## CF.sub.3                                                                            F F                                               11 CH.sub.3                                                                           1                                                                                ##STR704## CF.sub.2 H                                                                          F F                                               12 C.sub.2 H.sub.5                                                                    1                                                                                ##STR705## CF.sub.2 H                                                                          F F                                               13 C.sub.3 H.sub.7                                                                    1                                                                                ##STR706## CF.sub.2 H                                                                          F F                                               14 C.sub.4 H.sub.9                                                                    1                                                                                ##STR707## CF.sub.2 H                                                                          F F                                               15 C.sub.5 H.sub.11                                                                   1                                                                                ##STR708## CF.sub.2 H                                                                          F F                                               16 CH.sub.3                                                                           1                                                                                ##STR709## OCF.sub.3                                                                           F F                                               17 C.sub.2 H.sub.5                                                                    1                                                                                ##STR710## OCF.sub.3                                                                           F F Cr room temp. or lower Iso                    18 C.sub.3 H.sub.7                                                                    1                                                                                ##STR711## OCF.sub.3                                                                           F F                                               19 C.sub.4 H.sub.9                                                                    1                                                                                ##STR712## OCF.sub.3                                                                           F F                                               20 C.sub.5 H.sub.11                                                                   1                                                                                ##STR713## OCF.sub.3                                                                           F F                                               21 CH.sub.3                                                                           1                                                                                ##STR714## OCF.sub.2 H                                                                         F F                                               22 C.sub.2 H.sub.5                                                                    1                                                                                ##STR715## OCF.sub.2 H                                                                         F F                                               23 C.sub.3 H.sub.7                                                                    1                                                                                ##STR716## OCF.sub.2 H                                                                         F F                                               24 C.sub.4 H.sub.9                                                                    1                                                                                ##STR717## OCF.sub.2 H                                                                         F F                                               25 C.sub.5 H.sub.11                                                                   1                                                                                ##STR718## OCF.sub.2 H                                                                         F F                                               26 CH.sub.3                                                                           1                                                                                ##STR719## CFH.sub.2                                                                           F F                                               27 C.sub.2 H.sub.5                                                                    1                                                                                ##STR720## CFH.sub.2                                                                           F F                                               28 C.sub.3 H.sub.7                                                                    1                                                                                ##STR721## CFH.sub.2                                                                           F F                                               29 C.sub.4 H.sub.9                                                                    1                                                                                ##STR722## CFH.sub.2                                                                           F F                                               30 C.sub.5 H.sub.11                                                                   1                                                                                ##STR723## CFH.sub.2                                                                           F F                                               31 C.sub.3 H.sub.7                                                                    1                                                                                ##STR724## CN    F F                                               32 C.sub.4 H.sub.9                                                                    1                                                                                ##STR725## CF.sub.3                                                                            F F                                               33 C.sub.5 H.sub.11                                                                   1                                                                                ##STR726## OCF.sub.3                                                                           F F                                               34 C.sub.10 H.sub.21                                                                  1                                                                                ##STR727## CN    F F                                               35 C.sub.7 H.sub.15                                                                   1                                                                                ##STR728## CF.sub.3                                                                            F F                                               36 C.sub.6 H.sub.13                                                                   1                                                                                ##STR729## OCF.sub.3                                                                           F F                                               37 C.sub.3 H.sub.7                                                                    1                                                                                ##STR730## CN    F F                                               38 C.sub.4 H.sub.9                                                                    1                                                                                ##STR731## CF.sub.3                                                                            F F                                               39 C.sub.5 H.sub.11                                                                   1                                                                                ##STR732## OCF.sub.3                                                                           F F                                               40 C.sub.2 H.sub.5                                                                    1                                                                                ##STR733## CN    F F                                               41 C.sub.7 H.sub.15                                                                   1                                                                                ##STR734## CF.sub.2 H                                                                          F F                                               42 C.sub.8 H.sub.17                                                                   1                                                                                ##STR735## OCF.sub.2 H                                                                         F F                                               __________________________________________________________________________

Example 2

Preparation of 3,5-difluoro-4-cyanophenyl 2-fluoro-4-(propoxymethyl)benzoate (in the formula (1), R=C₃ H₇, l=1, m=1,n and o=both, 0, A₁ =2-fluoro-1,4-phenylene group, Z₁ =--COO--, X=CN andY₁ and Y₂ =both, F) (Compound No. 43)

2-Fluoro-4-(propoxymethyl)benzoic acid (1.5 g, 7.1 mmol) was mixed withthionyl chloride (1.3 g, 10.6 mmol), pyridine (0.1 ml) and toluene (3ml), followed by reacting them at 80° C. for 2 hours, and distilling offsuperfluous thionyl chloride and toluene under reduced pressure, toobtain raw 2-fluoro-4-(propoxymethyl)benzoyl chloride.

Next, 2,6-difluoro-4-hydroxybenzonitrile (1.1 g, 7.1 mmol), pyridine(0.8 ml) and toluene (2 ml) were mixed. To this mixture was dropwiseadded a toluene 3 ml solution of the above2-fluoro-4-(propoxymethyl)benzoyl chloride at room temperature for 10minutes, followed by reacting them at 50° C. for 2 hours, adding water(10 ml) to the reaction product, extracting with toluene (50 ml),washing the resulting organic layer three times with 6N-HCl, three timeswith 2N-NaOH and three times with water, drying over anhydrous magnesiumsulfate, distilling off the solvent under reduced pressure, subjectingthe residue to silica gel column chromatography (eluent: toluene), toobtain raw 3,5-difluoro-4-cyanophenyl2-fluoro-4-(propoxymethyl)-benzoate (2.4 g) and recrystallizing thisproduct from heptane/ether (8/2), to obtain the captioned compound (1.6g, yield: 64.8%). Cr 23.5-24.3 Iso

Further, the mass Spector data well supported its structure.

Mass analysis: 350 (M+1)

According to the process of Example 2, the following compounds (No. 44to No. 88) are prepared.

    ______________________________________                                        No. R        1     A             X       Y.sub.1                                                                           Y.sub.2                          ______________________________________                                        44  C.sub.2 H.sub.5                                                                        1                                                                                    ##STR736##   CN      F   F                                45  C.sub.4 H.sub.9                                                                        1                                                                                    ##STR737##   CN      F   F                                46  C.sub.5 H.sub.11                                                                       1                                                                                    ##STR738##   CN      F   F                                47  CH.sub.3 5                                                                                    ##STR739##   CN      F   F                                48  C.sub.4 H.sub.9                                                                        2                                                                                    ##STR740##   CN      F   F                                49  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR741##   CN      F   F                                50  C.sub.4 H.sub.9                                                                        1                                                                                    ##STR742##   CN      F   F                                51  CH.sub.3 4                                                                                    ##STR743##   CN      F   F                                52  C.sub.5 H.sub.11                                                                       5                                                                                    ##STR744##   CN      F   F                                53  CH.sub.3 1                                                                                    ##STR745##   CF.sub.3                                                                              F   F                                54  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR746##   CF.sub.3                                                                              F   F                                55  C.sub.4 H.sub.9                                                                        1                                                                                    ##STR747##   CF.sub.3                                                                              F   F                                66  C.sub.3 H.sub.7                                                                        3                                                                                    ##STR748##   OCF.sub.3                                                                             F   F                                67  C.sub.2 H.sub.5                                                                        1                                                                                    ##STR749##   OCF.sub.3                                                                             F   F                                68  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR750##   OCF.sub.3                                                                             F   F                                69  CH.sub.3 2                                                                                    ##STR751##   OCF.sub.3                                                                             F   F                                70  C.sub.4 H.sub.9                                                                        4                                                                                    ##STR752##   OCF.sub.3                                                                             F   F                                71  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR753##   OCF.sub.2 H                                                                           F   F                                72  C.sub.4 H.sub.9                                                                        2                                                                                    ##STR754##   OCF.sub.2 H                                                                           F   F                                73  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR755##   OCF.sub.2 H                                                                           F   F                                74  C.sub.5 H.sub.11                                                                       5                                                                                    ##STR756##   OCF.sub.2 H                                                                           F   F                                75  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR757##   CF.sub.2 H                                                                            F   F                                76  C.sub.5 H.sub.11                                                                       1                                                                                    ##STR758##   CF.sub.2 H                                                                            F   F                                77  C.sub.9 H.sub.19                                                                       1                                                                                    ##STR759##   CF.sub.2 H                                                                            F   F                                78  C.sub.5 H.sub.11                                                                       2                                                                                    ##STR760##   CF.sub.2 H                                                                            F   F                                79  C.sub.2 H.sub.5                                                                        1                                                                                    ##STR761##   CF.sub.2 H                                                                            F   F                                80  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR762##   CF.sub.2 H                                                                            F   F                                81  CH.sub.3 2                                                                                    ##STR763##   CF.sub.2 H                                                                            F   F                                82  C.sub.3 H.sub.7                                                                        3                                                                                    ##STR764##   CF.sub.2 H                                                                            F   F                                83  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR765##   CFH.sub.2                                                                             F   F                                84  C.sub.5 H.sub.11                                                                       1                                                                                    ##STR766##   CFH.sub.2                                                                             F   F                                85  C.sub.2 H.sub.5                                                                        9                                                                                    ##STR767##   CFH.sub.2                                                                             F   F                                86  C.sub.3 H.sub.7                                                                        1                                                                                    ##STR768##   CFH.sub.2                                                                             F   F                                87  CH.sub.3 2                                                                                    ##STR769##   CFH.sub.2                                                                             F   F                                88  C.sub.3 H.sub.7                                                                        3                                                                                    ##STR770##   CFH.sub.2                                                                             F   F                                ______________________________________                                    

Example 3

Preparation of 3,5-difluoro-4-cyanophenyl 4-(ethoxyethyl)benzoate (inthe formula (1), R=C₂ H₅, l=2, m=1, n and o=both, 0, A₁ =1,4-phenylenegroup, Z₁ =--COO--, X=CN, and Y₁ and Y₂ =both, F) (Compound No. 89)

4-(Ethoxyethyl)benzoic acid (1.4 g, 7.2 mmol) was mixed with thionylchloride (1.3 g, 10.8 mmol), pyridine (0.1 ml) and toluene (4 ml),followed by reacting them at 80° C. for 2 hours, distilling superfluousthionyl chloride and toluene under reduced pressure, to obtain raw4-(ethoxy-ethyl)benzoyl chloride.

Next, 2,6-difluoro-4-hydroxybenzonitrile (1.1 g, 7.2 mmol), pyridine(0.8 ml) and toluene (2 ml) were mixed. To this mixture was dropwiseadded a toluene 3 ml solution of the above 4-(ethoxyethyl)benzoylchloride, at room temperature for 5 minutes, followed by reacting themat 50° C. for 3 hours, adding water (15 ml) to the reaction product,extracting with toluene (50 ml), washing the resulting organic layerthree times with 6N-HCl, three times with 2N-NaOH and three times withwater, drying over anhydrous magnesium sulfate, distilling off thesolvent under reduced pressure, subjecting the resulting residue tosilica gel column chromatography (eluent: toluene), to obtain raw3,5-difluoro-4-cyanophenyl 4-(ethoxyethyl)benzoate (2.2 g), andrecrystallizing this product from heptane/ether (8/2), to obtain thecaptioned compound (1.5 g, yield: 62.8%).

Further, the mass Spector data well supported its structure.

Mass analysis: 332 (M+1)

According to the process of Example 3, the following compounds (No. 90to No. 107) are prepared.

    ______________________________________                                        No.  R       1     A             X       Y.sub.1                                                                           Y.sub.2                          ______________________________________                                        90   CH.sub.3                                                                              5                                                                                    ##STR771##   CN      F   F                                91   C.sub.2 H.sub.5                                                                       3                                                                                    ##STR772##   CN      F   F                                92   C.sub.4 H.sub.9                                                                       3                                                                                    ##STR773##   CN      F   F                                93   CH.sub.3                                                                              9                                                                                    ##STR774##   CF3     F   F                                94   C.sub.3 H.sub.7                                                                       2                                                                                    ##STR775##   CF3     F   F                                95   C.sub.5 H.sub.11                                                                      5                                                                                    ##STR776##   CF.sub.3                                                                              F   F                                96   C.sub.2 H.sub.5                                                                       2                                                                                    ##STR777##   CF.sub.2 H                                                                            F   F                                97   C.sub.3 H.sub.7                                                                       3                                                                                    ##STR778##   CF.sub.2 H                                                                            F   F                                98   C.sub.4 H.sub.9                                                                       5                                                                                    ##STR779##   CF.sub.2 H                                                                            F   F                                99   CH.sub.3                                                                              2                                                                                    ##STR780##   CFH.sub.2                                                                             F   F                                100  CH.sub.3                                                                              3                                                                                    ##STR781##   CFH.sub.2                                                                             F   F                                101  C.sub.10 H.sub.21                                                                     9                                                                                    ##STR782##   CFH.sub.2                                                                             F   F                                102  CH.sub.3                                                                              4                                                                                    ##STR783##   OCF.sub.3                                                                             F   F                                103  C.sub.3 H.sub.7                                                                       2                                                                                    ##STR784##   OCF.sub.3                                                                             F   F                                104  C.sub.5 H.sub.11                                                                      2                                                                                    ##STR785##   OCF.sub.3                                                                             F   F                                105  C.sub.2 H.sub.5                                                                       5                                                                                    ##STR786##   OCF.sub.2 H                                                                           F   F                                106  C.sub.4 H.sub.9                                                                       4                                                                                    ##STR787##   OCF.sub.2 H                                                                           F   F                                107  C.sub.5 H.sub.11                                                                      2                                                                                    ##STR788##   OCF.sub.2 H                                                                           F   F                                ______________________________________                                    

Example 4

Preparation of 3', 5'-difluoro-4'-cyanobiphenyl-4-yl4-(propoxymethyl)benzoate (in the formula (1), R=C₃ H₇, l=1, m andn=both, 1, o=0, A₁ and A₂ =both, 1,4-phenylene group, Z₁ =--COO--, Z₂=covalent bond, X=CN, and Y₁ and Y₂ =both, F) (Compound No. 108)4-(Propoxymethyl)benzoic acid (1.0 g, 5.2 mmol), 3',5'-difluoro-4'-cyano-4-hydroxybiphenyl (1.2 g, 5.2 mmol), DAMP (0.2 g,1.6 mmol) and dichloromethane (20 ml) were mixed, followed by dropwiseadding to the mixture, a dichloromethane 6 ml solution of DCC (1.3 g,6.2 mmol), at room temperature for 5 minutes, stirring them as it was,for 12 hours, filtering off deposited crystals, adding toluene (50 ml)to the filtrate, washing the resulting organic layer three times with6N-HCl, three times with 2N-NaOH and three times with water, drying overanhydrous magnesium sulfate, distilling off the solvent under reducedpressure, subjecting the residue to silica gel column chromatography(eluent: toluene), to obtain raw 3',5'-difluoro-4'-cyanobiphenyl-4-yl4-(propoxymethyl)-benzoate (2.7 g), and recrystallizing this productfrom heptane/ethyl acetate (7/3), to obtain the captioned compound (1.2g, yield: 48.3%).

Cr 91.9 to 92.8 N 121.2 Iso

Further, the mass spector data well supported its structure.

Mass analysis: 408 (M+1)

According to the process of Example 4, the following pounds (No. 109 toNo. 147) are prepared.

    __________________________________________________________________________    No.                                                                              R    1 A                 X     Y.sub.1                                                                         Y.sub.2                                   __________________________________________________________________________    109                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR789##       CN    F F                                         110                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR790##       CN    F F                                         111                                                                              CH.sub.3                                                                           2                                                                                ##STR791##       CN    F F                                         112                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR792##       CN    F F                                         113                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR793##       CN    F F                                         114                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR794##       CF.sub.3                                                                            F F                                         115                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR795##       CF.sub.3                                                                            F F Cr 91.4-92.2 SA 102.3- 103.7 Iso        116                                                                              C.sub.3 H.sub.7                                                                    3                                                                                ##STR796##       CF.sub.3                                                                            F F                                         117                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR797##       CF.sub.3                                                                            F F                                         118                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR798##       CF.sub.3                                                                            F F                                         119                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR799##       CF.sub.2 H                                                                          F F                                         120                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR800##       CF.sub.2 H                                                                          F F                                         121                                                                              C.sub.5 H.sub.11                                                                   4                                                                                ##STR801##       CF.sub.2 H                                                                          F F                                         122                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR802##       CF.sub.2 H                                                                          F F                                         123                                                                              CH.sub.3                                                                           1                                                                                ##STR803##       CF.sub.2 H                                                                          F F                                         124                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR804##       OCF.sub.3                                                                           F F                                         125                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR805##       OCF.sub.3                                                                           F F                                         126                                                                              C.sub.2 H.sub.5                                                                    4                                                                                ##STR806##       OCF.sub.3                                                                           F F                                         127                                                                              CH.sub.3                                                                           1                                                                                ##STR807##       OCF.sub.3                                                                           F F                                         128                                                                              C.sub.4 H.sub.9                                                                    5                                                                                ##STR808##       OCF.sub.3                                                                           F F                                         129                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR809##       OCF.sub.2 H                                                                         F F                                         130                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR810##       OCF.sub.2 H                                                                         F F                                         131                                                                              CH.sub.3                                                                           3                                                                                ##STR811##       OCF.sub.2 H                                                                         F F                                         132                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR812##       OCF.sub.2 H                                                                         F F                                         133                                                                              CH.sub.3                                                                           1                                                                                ##STR813##       OCF.sub.2 H                                                                         F F                                         134                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR814##       CFH.sub.2                                                                           F F                                         135                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR815##       CFH.sub.2                                                                           F F                                         136                                                                              C.sub.8 H.sub.17                                                                   5                                                                                ##STR816##       CFH.sub.2                                                                           F F                                         137                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR817##       CFH.sub.2                                                                           F F                                         138                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR818##       CFH.sub.2                                                                           F F                                         139                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR819##       CN    F F Cr 85.3-85.9 N 112.6 Iso                140                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR820##       CF.sub.3                                                                            F F                                         141                                                                              CH.sub.3                                                                           1                                                                                ##STR821##       CF.sub.2 H                                                                          F F                                         142                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR822##       OCF.sub.3                                                                           F F                                         143                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR823##       OCF.sub.2 H                                                                         F F                                         144                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR824##       CN    F F                                         145                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR825##       CF.sub.3                                                                            F F                                         146                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR826##       CF.sub.3                                                                            F F                                         147                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR827##       OCF.sub.3                                                                           F F                                         __________________________________________________________________________

Example 5

Preparation of trans-4-(3,5-difluoro-4-cyanophenyl)-cyclohexyl4-(butoxymethyl)benzoate (in the formula (1), R=C₄ H₉, l=1, m andn=both, 1, o=0, A₁ =1,4-phenylene group, A₂ =trans-1,4-cyclohexylenegroup, Z₁ =--COO--, Z₂ =covalent bond, X=CN, and Y₁ and Y₂ =both, F)(Compound No. 148) 4-(butoxymethyl)benzoic acid (1.5 g, 7.2 mmol) wasmixed with thionyl chloride (1.3 g, 10.8 mmol) pyridine (0.1 ml) andtoluene (3 ml), followed by reacting them at 80° C., for 2 hours, anddistilling off superfluous thionyl chloride and toluene under reducedpressure, to obtain raw 4-(butoxymethyl)benzoyl chloride.

Next, 4-(trans-4-hydroxycyclohexyl)-2,6-difluoro-benzonitrile (1.7 g,7.2 mmol), pyridine (0.8 ml) and toluene (2 ml) were mixed, followed bydropwise adding to the mixture, a toluene 3 ml solution of the above4-(butoxymethyl)benzoyl chloride, at room temperature for 10 minutes,reacting them at 50° C. for 2 hours, adding water (10 ml) to thereaction product, extracting with toluene (50 ml), washing the resultingorganic layer three times with 6N-HCl, three times with 2N-NaOH andthree times with water, drying over anhydrous magnesium sulfate,distilling off the solvent under reduced pressure, subjecting theresidue to silica gel column chromatography (eluent: toluene), to obtainraw trans-4'-(3,5-difluoro-4-cyanophenyl)cyclohexyl4-(butoxymethyl)benzoate (2.9 g), and recrystallizing this product fromheptane/ether (6/4), to obtain the captioned compound (2.3 g, yield:74.7%).

Further, the mass spector data well supported its structure.

Mass analysis: 428 (M+1)

According to the process of Example 5, the following compounds (No. 149to No. 186) are prepared:

    __________________________________________________________________________    No.                                                                              R    1 A                 X     Y.sub.1                                                                          Y.sub.2                                  __________________________________________________________________________    149                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR828##       CN    F  F                                        150                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR829##       CN    F  F                                        151                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR830##       CN    F  F                                        152                                                                              C.sub.2 H.sub.5                                                                    2                                                                                ##STR831##       CN    F  F                                        153                                                                              CH.sub.3                                                                           1                                                                                ##STR832##       CF3   F  F                                        154                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR833##       CF.sub.3                                                                            F  F                                        155                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR834##       CF.sub.3                                                                            F  F                                        156                                                                              C.sub.5 H.sub.11                                                                   9                                                                                ##STR835##       CF.sub.3                                                                            F  F                                        157                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR836##       CF.sub.2 H                                                                          F  F                                        158                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR837##       CF.sub.2 H                                                                          F  F                                        159                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR838##       CF.sub.2 H                                                                          F  F                                        160                                                                              C.sub.2 H.sub.5                                                                    3                                                                                ##STR839##       CF.sub.2 H                                                                          F  F                                        161                                                                              CH.sub.3                                                                           1                                                                                ##STR840##       OCF.sub.3                                                                           F  F                                        162                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR841##       OCF.sub.3                                                                           F  F                                        163                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR842##       OCF.sub.3                                                                           F  F                                        164                                                                              C.sub.4 H.sub.9                                                                    2                                                                                ##STR843##       OCF.sub.3                                                                           F  F                                        165                                                                              CH.sub.3                                                                           1                                                                                ##STR844##       OCF.sub.2 H                                                                         F  F                                        166                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR845##       OCF.sub.2 H                                                                         F  F                                        167                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR846##       OCF.sub.2 H                                                                         F  F                                        168                                                                              C.sub.10 H.sub.21                                                                  4                                                                                ##STR847##       OCF.sub.2 H                                                                         F  F                                        169                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR848##       CFH.sub.2                                                                           F  F                                        170                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR849##       CFH.sub.2                                                                           F  F                                        171                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR850##       CFH.sub.2                                                                           F  F                                        172                                                                              C.sub.6 H.sub.13                                                                   2                                                                                ##STR851##       CFH.sub.2                                                                           F  F                                        173                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR852##       CFH.sub.2                                                                           F  F                                        174                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR853##       CN    F  F                                        175                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR854##       CN    F  F                                        176                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR855##       CF.sub.3                                                                            F  F                                        177                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR856##       CF.sub.3                                                                            F  F                                        178                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR857##       CF.sub.3                                                                            F  F                                        179                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR858##       CF.sub.2 H                                                                          F  F                                        180                                                                              C.sub.3 H.sub.7                                                                    3                                                                                ##STR859##       CF.sub.2 H                                                                          F  F                                        181                                                                              CH.sub.3                                                                           1                                                                                ##STR860##       OCF.sub.3                                                                           F  F                                        182                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR861##       OCF.sub.3                                                                           F  F                                        183                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR862##       OCF.sub.2 H                                                                         F  F                                        184                                                                              C.sub.8 H.sub.17                                                                   2                                                                                ##STR863##       OCF.sub.2 H                                                                         F  F                                        185                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR864##       CFH.sub.2                                                                           F  F                                        186                                                                              CH.sub.3                                                                           7                                                                                ##STR865##       CFH.sub.2                                                                           F  F                                        __________________________________________________________________________

Example 6

Preparation of 3,5-difluoro-4-cyanophenyl4-(trans-4-(ethoxymethyl)cyclohexyl)benzoate (in the formula (1), R=C₂H₅, l=1, m and n=both, 1, o=0, A₁ =trans-1,4-cyclohexylene group, A₂=1,4-phenylene group, Z₁ =covalent bond, Z₂ =--COO--, X=CN, and Y₁ andY₂ =both, F) (Compound No. 187)4-(Trans-4-(ethoxymethyl)cyclohexyl)benzoic acid (1.9 g, 7.1 mmol) wasmixed with thionyl chloride (1.3 g, 10.6 mmol), pyridine (0.1 ml) andtoluene (4 ml), followed by reacting them at 80° C. for 2 hours, anddistilling off superfluous thionyl chloride and toluene under reducedpressure, to obtain raw 4-(trans-4-(ethoxymethyl)cyclohexyl)benzoylchloride.

Next, 2,6-difluoro-4-hydroxybenzonitrile (1.1 g, 7.1 mmol) was mixedwith pyridine (0.8 ml) and toluene (2 me), followed by dropwise addingto the mixture, a toluene 3 ml solution of the above4-(trans-4-(ethoxy-methyl)cyclohexyl)benzoyl chloride, at roomtemperature for 5 minutes, reacting them at 50° C., for 3 hours, addingwater (15 ml) to the reaction product, extracting with toluene (50 ml),washing the resulting organic layer three times with 6N-HCl, three timeswith 2N-NaOH and three times with water, drying over magnesium sulfate,distilling off the solvent under reduced pressure, subjecting theresidue to silica gel column chromatography (eluent: toluene), to obtainraw 3,5-difluoro-4-cyanophenyl4-(trans-4-(ethoxymethyl)cyclohexyl)benzoate (2.7 g), andrecrystallizing the product from heptane/ether (7/3), to obtain thecaptioned compound (2.2 g, yield: 77.7%).

Cr 75.1-75.8N 125.3 Iso

Further, the mass spector data well supported its structure.

Mass analysis: 400 (M+1)

According to the process of Example 6, the following compounds (No. 188to No. 228) are prepared:

    __________________________________________________________________________    No.                                                                              R    1 A                 X     Y.sub.1                                                                         Y.sub.2                                   __________________________________________________________________________    188                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR866##       CN    F F                                         189                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR867##       CN    F F                                         190                                                                              CH.sub.3                                                                           9                                                                                ##STR868##       CN    F F                                         191                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR869##       CN    F F                                         192                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR870##       CN    F F                                         193                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR871##       CF.sub.3                                                                            F F                                         194                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR872##       CF.sub.3                                                                            F F                                         195                                                                              C.sub.3 H.sub.7                                                                    3                                                                                ##STR873##       CF.sub.3                                                                            F F                                         196                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR874##       CF.sub.3                                                                            F F                                         197                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR875##       CF.sub.3                                                                            F F                                         198                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR876##       CF.sub.2 H                                                                          F F                                         199                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR877##       CF.sub.2 H                                                                          F F                                         200                                                                              C.sub.5 H.sub.11                                                                   4                                                                                ##STR878##       CF.sub.2 H                                                                          F F                                         201                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR879##       CF.sub.2 H                                                                          F F                                         202                                                                              CH.sub.3                                                                           1                                                                                ##STR880##       CF.sub.2 H                                                                          F F                                         203                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR881##       OCF.sub.3                                                                           F F                                         204                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR882##       OCF.sub.3                                                                           F F                                         205                                                                              C.sub.6 H.sub.13                                                                   4                                                                                ##STR883##       OCF.sub.3                                                                           F F                                         206                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR884##       OCF.sub.3                                                                           F F                                         207                                                                              C.sub.4 H.sub.9                                                                    5                                                                                ##STR885##       OCF.sub.3                                                                           F F                                         208                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR886##       OCF.sub.2 H                                                                         F F                                         209                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR887##       OCF.sub.2 H                                                                         F F                                         210                                                                              CH.sub.3                                                                           3                                                                                ##STR888##       OCF.sub.2 H                                                                         F F                                         211                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR889##       OCF.sub.2 H                                                                         F F                                         212                                                                              CH.sub.3                                                                           1                                                                                ##STR890##       OCF.sub.2 H                                                                         F F                                         213                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR891##       CFH.sub.2                                                                           F F                                         214                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR892##       CFH.sub.2                                                                           F F                                         215                                                                              CH.sub.3                                                                           6                                                                                ##STR893##       CFH.sub.2                                                                           F F                                         216                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR894##       CFH.sub.2                                                                           F F                                         217                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR895##       CFH.sub.2                                                                           F F                                         218                                                                              CH.sub.3                                                                           1                                                                                ##STR896##       CN    F F Cr 76.8-78.2 N 158.9 Iso                219                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR897##       CN    F F                                         220                                                                              CH.sub.3                                                                           1                                                                                ##STR898##       CF.sub.3                                                                            F F                                         221                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR899##       CF.sub.3                                                                            F F                                         222                                                                              C.sub.2 H.sub.5                                                                    1                                                                                ##STR900##       CF.sub.2 H                                                                          F F                                         223                                                                              C.sub.5 H.sub.11                                                                   5                                                                                ##STR901##       CF.sub.2 H                                                                          F F                                         224                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR902##       OCF.sub.3                                                                           F F                                         225                                                                              C.sub.5 H.sub.11                                                                   1                                                                                ##STR903##       OCF.sub.3                                                                           F F                                         226                                                                              C.sub.4 H.sub.9                                                                    1                                                                                ##STR904##       OCF.sub.2 H                                                                         F F                                         227                                                                              C.sub.8 H.sub.17                                                                   1                                                                                ##STR905##       OCF.sub.2 H                                                                         F F                                         228                                                                              C.sub.3 H.sub.7                                                                    1                                                                                ##STR906##       CFH.sub.2                                                                           F F                                         __________________________________________________________________________

Example 7

Preparation of 3,5-difluoro-4-cyanophenyl4'-(pentyloxymethyl)biphenyl-4-carboxylate (in the formula (1), R=C₅H₁₁, l=1, m and n=both, 1, o=0, A₁ and A₂ =both, 1,4-phenylene group, Z₁=covalent bond, Z₂ =--COO--, X=CN, and Y₁ and Y₂ =both, F) (Compound No.229) 4'-(Pentyloxymethyl)biphenyl-4-carboxyic acid (2.1 g, 7.0 mmol) wasmixed with thionyl chloride (1.3 g, 10.6 mmol), pyridine (0.1 ml) andtoluene (4 ml), followed by reacting them at 80° C. for 2 hours, anddistilling off superfluous thionyl chloride and toluene under reducedpressure, to obtain raw 4'-(pentyloxymethyl)biphenyl-4-carbonylchloride.

Next, 2,6-difluoro-4-hydroxybenzonitrile (1.1 g, 7.1 mmol) was mixedwith pyridine (0.8 ml) and toluene (2 ml), followed by dropwise addingto the mixture, a toluene 3 ml solution of the above4'-(pentyloxymethyl)-biphenyl-4-carbonyl chloride, at room temperaturefor 5 minutes, reacting them at 50° C. for 3 hours, adding water (15 ml)to the reaction product, extracting with toluene (50 ml), washing theresulting organic layer, three times with 6N-HCl, three times with2N-NaOH and three times with water, drying over anhydrous magnesiumsulfate, distilling off the solvent under reduced pressure, subjectingthe residue to silica gel column chromatography (eluent: toluene), toobtain raw 3,5-difluoro-4-cyano-phenyl4'-(pentyloxymethyl)biphenyl-4-carboxylate (2.9 g), and recrystallizingthis product from heptane/ether (1/1), to obtain the captioned compound(2.0 g, yield: 65.3%).

Further, the mass spector data well supported its structure.

Mass analysis: 436 (M+1)

According to the process of Example 7, the following compounds (No. 230to No. 270) are prepared:

    __________________________________________________________________________    No.                                                                              R   l  A                 X   Y.sub.1                                                                          Y.sub.2                                    __________________________________________________________________________    230                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR907##       CN  F  F                                          231                                                                              C.sub.2 H.sub.5                                                                   1                                                                                 ##STR908##       CN  F  F                                          232                                                                              C.sub.3 H.sub.7                                                                   2                                                                                 ##STR909##       CN  F  F                                          233                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR910##       CN  F  F                                          234                                                                              C.sub.5 H.sub.11                                                                  1                                                                                 ##STR911##       CN  F  F                                          235                                                                              CH.sub.3                                                                          1                                                                                 ##STR912##       CF.sub.3                                                                          F  F                                          236                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR913##       CF.sub.3                                                                          F  F                                          237                                                                              CH.sub.3                                                                          3                                                                                 ##STR914##       CF.sub.3                                                                          F  F                                          238                                                                              C.sub.2 H.sub.5                                                                   1                                                                                 ##STR915##       CF.sub.3                                                                          F  F                                          239                                                                              C.sub.4 H.sub.9                                                                   1                                                                                 ##STR916##       CF.sub.3                                                                          F  F                                          240                                                                              C.sub.2 H.sub.5                                                                   1                                                                                 ##STR917##       CF.sub.2 H                                                                        F  F                                          241                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR918##       CF.sub.2 H                                                                        F  F                                          242                                                                              C.sub.5 H.sub.11                                                                  4                                                                                 ##STR919##       CF.sub.2 H                                                                        F  F                                          243                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR920##       CF.sub.2 H                                                                        F  F                                          244                                                                              CH.sub.3                                                                          1                                                                                 ##STR921##       CF.sub.2 H                                                                        F  F                                          245                                                                              C.sub.4 H.sub.9                                                                   1                                                                                 ##STR922##       OCF.sub.3                                                                         F  F                                          246                                                                              C.sub.5 H.sub.11                                                                  1                                                                                 ##STR923##       OCF.sub.3                                                                         F  F                                          247                                                                              C.sub.2 H.sub.5                                                                   6                                                                                 ##STR924##       OCF.sub.3                                                                         F  F                                          248                                                                              CH.sub.3                                                                          1                                                                                 ##STR925##       OCF.sub.3                                                                         F  F                                          249                                                                              C.sub.4 H.sub.9                                                                   5                                                                                 ##STR926##       OCF.sub.3                                                                         F  F                                          250                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR927##       OCF.sub.2 H                                                                       F  F                                          251                                                                              C.sub.5 H.sub.11                                                                  1                                                                                 ##STR928##       OCF.sub.2 H                                                                       F  F                                          252                                                                              CH.sub.3                                                                          8                                                                                 ##STR929##       OCF.sub.2 H                                                                       F  F                                          253                                                                              C.sub.2 H.sub.5                                                                   1                                                                                 ##STR930##       OCF.sub.2 H                                                                       F  F                                          254                                                                              CH.sub.3                                                                          1                                                                                 ##STR931##       OCF.sub.2 H                                                                       F  F                                          255                                                                              CH.sub.3                                                                          1                                                                                 ##STR932##       CFH.sub.2                                                                         F  F                                          256                                                                              C.sub.4 H.sub.9                                                                   1                                                                                 ##STR933##       CFH.sub.2                                                                         F  F                                          257                                                                              C.sub.7 H.sub.15                                                                  1                                                                                 ##STR934##       CFH.sub.2                                                                         F  F                                          258                                                                              C.sub.2 H.sub.5                                                                   1                                                                                 ##STR935##       CFH.sub.2                                                                         F  F                                          259                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR936##       CFH.sub.2                                                                         F  F                                          260                                                                              C.sub.2 H.sub.5                                                                   1                                                                                 ##STR937##       CN  F  F                                          261                                                                              C.sub.4 H.sub.9                                                                   1                                                                                 ##STR938##       CN  F  F                                          262                                                                              CH.sub.3                                                                          4                                                                                 ##STR939##       CF.sub.3                                                                          F  F                                          263                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR940##       CF.sub.3                                                                          F  F                                          264                                                                              C.sub.5 H.sub.11                                                                  1                                                                                 ##STR941##       CF.sub.2 H                                                                        F  F                                          265                                                                              C.sub.3 H.sub.7                                                                   1                                                                                 ##STR942##       CF.sub.2 H                                                                        F  F                                          266                                                                              C.sub.4 H.sub.9                                                                   1                                                                                 ##STR943##       OCF.sub.3                                                                         F  F                                          267                                                                              C.sub.9 H.sub.19                                                                  1                                                                                 ##STR944##       OCF.sub.3                                                                         F  F                                          268                                                                              CH.sub.3                                                                          1                                                                                 ##STR945##       OCF.sub.2 H                                                                       F  F                                          269                                                                              C.sub.4 H.sub.9                                                                   1                                                                                 ##STR946##       OCF.sub.2 H                                                                       F  F                                          270                                                                              CH.sub.3                                                                          1                                                                                 ##STR947##       CFH.sub.2                                                                         F  F                                          __________________________________________________________________________

Example 8

Preparation of 3,5-difluoro-4-cyanophenyl4-(2-(trans-4-butoxymethyl)cyclohexyl)ethyl benzoate (in the formula(1), R=C₄ H₉, l=1, m and n=both, 1, A₁ =trans-1,4-cyclohexylene group,A₂ =1,4-phenylene group, Z₁ =--(CH₂)₂ --, Z₂ =--COO--, X=CN, and Y₁ andY₂ =both, F) (Compound No. 271)

4-(2-Trans-4-(butoxymethyl)cyclohexyl)ethyl)benzoic acid (2.1 g, 7.3mmol) was mixed with thionyl chloride (1.3 g, 10.9 mmol), pyridine (0.1ml) and toluene (3 ml), followed by reacting them at 80° C., for 3hours, and distilling off superfluous thionyl chloride and toluene underreduced pressure, to obtain raw 4-(2-(trans-4-(butoxymethyl)cyclohexyl)ethyl)benzoyl chloride.

Next, 2,6-difluoro-4-hydroxybenzonitrile (1.2 g, 7.4 mmol) was mixedwith pyridine (0.8 ml) and toluene (2 ml), followed by dropwise addingto the mixture, a toluene 3 ml solution of the above4-(2-(trans-4-(butoxymethyl)cyclohexyl)ethyl)benzoyl chloride at roomtemperature for 5 minutes, reacting them at 50° C. for 2 hours, addingwater (15 ml) to the reaction product, extracting with toluene (50 ml),washing the resulting organic layer three times with 6N-HCl, three timeswith 2N-NaOH and three times with water, drying over anhydrous magnesiumsulfate, distilling off the solvent under reduced pressure, subjectingthe residue to silica gel column chromatography (eluent: toluene), toobtain raw 3,5-difluoro-4-cyanophenyl4-(2-(trans-4-(butoxymethyl)-cyclohexyl) ethyl)benzoate (2.8 g), andrecrystallizing the product from heptane/ether (7/3), to obtain thecaptioned compound (2.5 g, yield: 80.6%).

Further, the mass spector data well supported its structure.

Mass analysis: 456 (M+1)

According to the process of Example 8, the following compounds (No. 272to No. 293) are prepared:

    __________________________________________________________________________    No.                                                                              R   l A                           X   Y.sub.1                                                                         Y.sub.2                            __________________________________________________________________________    272                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR948##                 CN  F F                                  273                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR949##                 CN  F F                                  274                                                                              CH.sub.3                                                                          2                                                                                ##STR950##                 CF.sub.3                                                                          H F                                  275                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR951##                 CF.sub.3                                                                          F F                                  276                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR952##                 CF.sub.3                                                                          H H                                  277                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR953##                 CF.sub.2 H                                                                        F F                                  278                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR954##                 CF.sub.2 H                                                                        F F                                  279                                                                              CH.sub.3                                                                          1                                                                                ##STR955##                 OCF.sub.3                                                                         F F                                  280                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR956##                 OCF.sub.3                                                                         F F                                  281                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR957##                 OCF.sub.2 H                                                                       F F                                  282                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR958##                 CFH.sub.2                                                                         F F                                  283                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR959##                 CN  F F                                  284                                                                              CH.sub.3                                                                          1                                                                                ##STR960##                 CF.sub.3                                                                          F F                                  285                                                                              C.sub.3 H.sub.9                                                                   1                                                                                ##STR961##                 CF.sub.3                                                                          H F                                  286                                                                              C.sub.7 H.sub.15                                                                  1                                                                                ##STR962##                 CF.sub.2 H                                                                        F F                                  287                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR963##                 OCF.sub.3                                                                         F F                                  288                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR964##                 OCF.sub.2 H                                                                       F F                                  289                                                                              CH.sub.3                                                                          1                                                                                ##STR965##                 CN  F F                                  290                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR966##                 CF.sub.3                                                                          F F                                  291                                                                              C.sub.5 H.sub.11                                                                  7                                                                                ##STR967##                 CFH.sub.2                                                                         F F                                  292                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR968##                 OCF.sub.3                                                                         F F                                  293                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR969##                 OCF.sub.2 H                                                                       F F                                  __________________________________________________________________________

Example 9

Preparation of 3', 5'-difluoro-4'-cyanobiphenyl-4-yl4-(trans-4-(propoxymethyl)cyclohexyl)benzoate (in the formula (1), R=C₃H₇, l=1, m, n and o=either, 1, A₁ =trans-1,4-cyclohexylene group, A₂ andA₃ =both, 1,4-phenylene group, Z₁ and Z₃ =both covalent bond, Z₂=--COO--, X=CN, and Y₁ and Y₂ =both, F) (Compound No. 294)

4-(Trans-4-(propoxymethyl)cyclohexyl)benzoic acid (2.0 g, 7.2 mmol) wasmixed with thionyl chloride (1.3 g, 10.9 mmol), pyridine (0.1 ml) andtoluene (4 ml), followed by reacting them at 80° C. for 2 hours, anddistilling off superfluous thionyl chloride and toluene under reducedpressure, to obtain raw 4-(trans-4-(propoxymethyl)cyclohexyl) benzoylchloride.

Next, 3',5'-difluoro-4'-cyano-4-hydroxybiphenyl (1.7 g, 7.2 mmol) wasmixed with pyridine (0.8 ml) and toluene (3 ml), followed by dropwiseadding to the mixture, a toluene 3 ml solution of the above4-(trans-4-(propoxymethyl) cyclohexyl)benzoyl chloride, at roomtemperature for 5 minutes, reacting the mixture at 50° C. for 3 hours,adding water (15 ml) to the reaction product, extracting with toluene(50 ml), washing the resulting organic layer, three times with 6N-HCl,three times with 2N-NaOH and three times with water, drying overanhydrous magnesium sulfate, distilling off the solvent under reducedpressure, subjecting the residue to silica gel column chromatography(eluent: toluene), to obtain raw 3',5'-difluoro-4'-cyanobiphenyl-4-yl4-(trans-4-(propoxymethyl)cyclohexyl)-benzoate (3.4 g), andrecrystallizing this product from heptane/ether (1/1), to obtain thecaptioned compound (2.8 g, yield: 79.0%).

Further, the mass spector data well supported its structure.

Mass analysis: 490 (M+1)

According to the process of Example 9, the following compounds (No. 295to No. 334) are prepared:

    __________________________________________________________________________    No.                                                                              R   l A                        X   Y.sub.1                                                                         Y.sub.2                               __________________________________________________________________________    295                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR970##              CN  F F                                     296                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR971##              CN  F F                                     297                                                                              CH.sub.3                                                                          2                                                                                ##STR972##              CN  F F                                     298                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR973##              CN  F F                                     299                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR974##              CN  F F                                     300                                                                              CH.sub.3                                                                          1                                                                                ##STR975##              CF.sub.3                                                                          F F Cr 185.3-189.3 N 224.5 Iso          301                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR976##              CF.sub.3                                                                          F F Cr 84.1-84.9 N 191.0 Iso            302                                                                              C.sub.3 H.sub.7                                                                   3                                                                                ##STR977##              CF.sub.3                                                                          F F                                     303                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR978##              CF.sub.3                                                                          F F                                     304                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR979##              CF.sub.3                                                                          F F                                     305                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR980##              CF.sub.2 H                                                                        F F                                     306                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR981##              CF.sub.2 H                                                                        F F                                     307                                                                              C.sub.8 H.sub.17                                                                  8                                                                                ##STR982##              CF.sub.2 H                                                                        F F                                     308                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR983##              CF.sub.2 H                                                                        F F                                     309                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR984##              CF.sub.2 H                                                                        F F                                     310                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR985##              OCF.sub.3                                                                         F F                                     311                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR986##              OCF.sub.3                                                                         F F                                     312                                                                              C.sub.2 H.sub.5                                                                   4                                                                                ##STR987##              OCF.sub.3                                                                         F F                                     313                                                                              CH.sub.3                                                                          1                                                                                ##STR988##              OCF.sub.3                                                                         F F                                     314                                                                              C.sub.4 H.sub.9                                                                   5                                                                                ##STR989##              OCF.sub.3                                                                         F F                                     315                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR990##              OCF.sub.2 H                                                                       F F                                     316                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR991##              OCF.sub.2 H                                                                       F F                                     317                                                                              CH.sub.3                                                                          6                                                                                ##STR992##              OCF.sub.2 H                                                                       F F                                     318                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR993##              OCF.sub.2 H                                                                       F F                                     319                                                                              CH.sub.3                                                                          1                                                                                ##STR994##              OCF.sub.2 H                                                                       F F                                     320                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR995##              CFH.sub.2                                                                         F F                                     321                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR996##              CFH.sub.2                                                                         F F                                     322                                                                              C.sub.10 H.sub.21                                                                 1                                                                                ##STR997##              CFH.sub.2                                                                         F F                                     323                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR998##              CFH.sub.2                                                                         F F                                     324                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR999##              CFH.sub.2                                                                         F F                                     325                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1000##             OCF.sub.3                                                                         F F                                     326                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1001##             OCF.sub.2 H                                                                       F F                                     327                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1002##             CN  F F                                     328                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1003##             CFH.sub.2                                                                         F F                                     329                                                                              C.sub.7 H.sub.15                                                                  1                                                                                ##STR1004##             CF.sub.2 H                                                                        F F                                     330                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1005##             OCF.sub.3                                                                         F F                                     331                                                                              CH.sub.3                                                                          4                                                                                ##STR1006##             OCF.sub.2 H                                                                       F F                                     332                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1007##             CN  F F                                     333                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1008##             CF.sub.3                                                                          F F                                     334                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1009##             OCF.sub.3                                                                         F F                                     __________________________________________________________________________

Example 10

Preparation of 4-(trifluoromethyl)phenyl 4-(propoxymethyl) benzoate (inthe formula (1), R=C₃ H₇, l=1, m=1, n and o=both, 0, A₁ =1,4-phenylenegroup, Z₁ =--COO--, X=CF₃, and Y₁ and Y₂ =both, H) (Compound No. 335)

4-(Propoxymethyl)benzoic acid (1.4 g, 7.2 mmol) was mixed with thionylchloride (1.3 g, 10.9 mmol), pyridine (0.1 ml) and toluene (3 ml),followed by reacting them at 80° C. for 2 hours, and distilling offsuperfluous thionyl chloride and toluene under reduced pressure, toobtain raw 4-(propoxymethyl) benzoyl chloride.

Next, 4-(trifluoromethyl)phenol (1.2 g, 7.4 mmol) was mixed withpyridine (0.8 ml) and toluene (2 ml), followed by dropwise adding to themixture, a toluene 3 ml solution of the above 4-(propoxymethyl)benzoylchloride at room temperature for 5 minutes, reacting them at 50° C. for2 hours, adding water (15 ml), extracting with toluene (30 ml), washingthe resulting organic layer three times with 6N-HCl, three times with2N-NaOH and three times with water, drying over anhydrous magnesiumsulfate, distilling off the solvent under reduced pressure, subjectingthe residue to silica gel column chromatography (eluent: toluene), toobtain raw 4-(trifluoromethyl)phenyl 4-propoxymethyl) benzoate (2.1 g),and recrystallizing this product from heptane/ether (8/2), to obtain thecaptioned compound (1.7 g, yield: 70.8%).

Further, the mass Spector data well supported its structure.

Mass analysis: 339 (M+1)

According to the process of Example 10, the following compounds (No. 336to No. 409) are prepared:

    __________________________________________________________________________    No.                                                                              R   l A                        X   Y.sub.1                                                                         Y.sub.2                               __________________________________________________________________________    336                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1010##             CF.sub.3                                                                          H H                                     337                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1011##             CF.sub.3                                                                          H F                                     338                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1012##             CF.sub.3                                                                          H F                                     339                                                                              CH.sub.3                                                                          5                                                                                ##STR1013##             CF.sub.3                                                                          H F                                     340                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1014##             CF.sub.3                                                                          H H                                     341                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1015##             CF.sub.3                                                                          H H                                     342                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1016##             CF.sub.3                                                                          H F                                     343                                                                              C.sub.9 H.sub.19                                                                  1                                                                                ##STR1017##             CF.sub.3                                                                          H F                                     344                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1018##             CF.sub.3                                                                          H F                                     345                                                                              CH.sub.3                                                                          1                                                                                ##STR1019##             CF.sub.3                                                                          H H                                     346                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1020##             CF.sub.3                                                                          H F                                     347                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1021##             CF.sub.3                                                                          H H                                     348                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1022##             CF.sub.3                                                                          H F                                     349                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1023##             CF.sub.3                                                                          H H                                     350                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1024##             CF.sub.3                                                                          H H Cr 69.6-70.2 S.sub.A 72.9- 73.1                                               N 75.6 Iso                          351                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1025##             CF.sub.3                                                                          H F                                     352                                                                              CH.sub.3                                                                          1                                                                                ##STR1026##             CF.sub.3                                                                          H H                                     353                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1027##             CF.sub.3                                                                          H H                                     354                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1028##             CF.sub.3                                                                          H H                                     355                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1029##             CF.sub.3                                                                          H F                                     356                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1030##             CF.sub.3                                                                          H H                                     357                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1031##             CF.sub.3                                                                          H F                                     358                                                                              CH.sub.3                                                                          1                                                                                ##STR1032##             CF.sub.3                                                                          H F                                     359                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1033##             CF.sub.3                                                                          H H                                     360                                                                              C.sub.6 H.sub.13                                                                  1                                                                                ##STR1034##             CF.sub.3                                                                          H F                                     361                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1035##             CF.sub.3                                                                          H H                                     362                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1036##             CF.sub.3                                                                          H F                                     363                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1037##             CF.sub.3                                                                          H H                                     364                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1038##             CF.sub.3                                                                          H F                                     365                                                                              CH.sub.3                                                                          1                                                                                ##STR1039##             CF.sub.3                                                                          H H                                     366                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1040##             CF.sub.3                                                                          H H                                     367                                                                              C.sub.3 H.sub.7                                                                   7                                                                                ##STR1041##             CF.sub.3                                                                          H F                                     368                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1042##             CF.sub.3                                                                          H H                                     369                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1043##             CF.sub.3                                                                          H H                                     370                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1044##             CF.sub.3                                                                          H H                                     371                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1045##             CF.sub.3                                                                          H F                                     372                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1046##             CF.sub.3                                                                          H F                                     373                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1047##             OCF.sub.2 H                                                                       H H                                     374                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1048##             OCF.sub.3                                                                         H H Cr 68.2-68.5 Iso                    375                                                                              C.sub.2 H.sub.5                                                                   7                                                                                ##STR1049##             CFH.sub.2                                                                         H F                                     376                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1050##             OCF.sub.3                                                                         H F Cr 30.5-31.8 Iso                    377                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1051##             OCF.sub.2 H                                                                       H H                                     378                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1052##             CFH.sub.2                                                                         H H                                     379                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1053##             CF.sub.2 H                                                                        H F                                     380                                                                              C.sub.9 H.sub.19                                                                  1                                                                                ##STR1054##             OCF.sub.2 H                                                                       H F                                     381                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1055##             OCF.sub.3                                                                         H F                                     382                                                                              CH.sub.3                                                                          1                                                                                ##STR1056##             CFH.sub.2                                                                         H H                                     383                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1057##             CF.sub.2 H                                                                        H F                                     384                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1058##             CFH.sub.2                                                                         H H                                     385                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1059##             OCF.sub.2 H                                                                       H F                                     386                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1060##             CFH.sub.2                                                                         H H                                     387                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1061##             OCF.sub.3                                                                         H F Cr 75.1-76.0(SA 61.7) N 96.2                                                  Iso                                 388                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1062##             CF.sub.2 H                                                                        H F                                     389                                                                              CH.sub.3                                                                          1                                                                                ##STR1063##             OCF.sub.3                                                                         H H                                     390                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1064##             CF.sub.2 H                                                                        H H                                     391                                                                              CH.sub.3                                                                          1                                                                                ##STR1065##             OCF.sub.3                                                                         H H                                     392                                                                              CH.sub.3                                                                          1                                                                                ##STR1066##             OCF.sub.3                                                                         H F Cr 47.7-48.9 N 146.0 Iso            393                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1067##             OCF.sub.3                                                                         H H                                     394                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1068##             CF.sub.2 H                                                                        H F                                     395                                                                              CH.sub.3                                                                          1                                                                                ##STR1069##             OCF.sub.3                                                                         H H                                     396                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1070##             OCF.sub.2 H                                                                       H H                                     397                                                                              C.sub.7 H.sub.15                                                                  1                                                                                ##STR1071##             CFH.sub.2                                                                         H F                                     398                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1072##             CF.sub.2 H                                                                        H H                                     399                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1073##             OCF.sub.3                                                                         H F                                     400                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1074##             CFH.sub.2                                                                         H F                                     401                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1075##             OCF.sub.3                                                                         H F                                     402                                                                              CH.sub.3                                                                          3                                                                                ##STR1076##             CF.sub.2 H                                                                        H F                                     403                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1077##             OCF.sub.2 H                                                                       H H                                     404                                                                              C.sub.3 H.sub.7                                                                   2                                                                                ##STR1078##             OCF.sub.3                                                                         H F                                     405                                                                              C.sub.2 H.sub.5                                                                   1                                                                                ##STR1079##             CFH.sub.2                                                                         H F                                     406                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1080##             OCF.sub.2 H                                                                       H H                                     407                                                                              C.sub.3 H.sub.7                                                                   1                                                                                ##STR1081##             OCF.sub.3                                                                         H H                                     408                                                                              C.sub.4 H.sub.9                                                                   1                                                                                ##STR1082##             CF.sub.2 H                                                                        H F                                     409                                                                              C.sub.5 H.sub.11                                                                  1                                                                                ##STR1083##             CFH.sub.2                                                                         H f                                     __________________________________________________________________________

Hereinafter, examples using the compound of the present invention as acomponent of liquid crystal compositions will be described.

In the use examples, NI, Δε, Δn, η and V₁₀, respectively representclearing point (°C.), dielectric anisotropy value, optical anisotropyvalue, viscosity at 20° C. (mPa·s) and threshold voltage (V).

Example 11 (Use Example 1)

A liquid crystal composition consisting of the followingcyanophenylcyclohexane group compounds:

4-(trans-4-propylcyclohexyl)benzonitrile 24% by weight,

4-(trans-4-pentylcyclohexyl)benzonitrile 36% by weight,

4-(trans-4-heptylcyclohexyl)benzonitrile 25% by weight,

and 4-(trans-4-pentylcyclohexyl)-4'-cyanobiphenyl 15% by weight,

has the following physical properties:

NI: 72.4, Δε: 11.0, Δn: 0.137, η: 27.0 and

a V₁₀ in a cell thickness of 9 μm: 1.78.

Compound No. 4 (15% by weight) was blended with the above composition(85% by weight), to obtain a nematic liquid crystal composition (a). Thevalues of the physical properties of this liquid crystal compositionwere as follows:

NI: 54.8, Δε: 16.9, Δn: 0.130, η: 31.9 and

V₁₀ in a cell thickness of 8.8 μm: 1.02.

This composition was allowed to stand in a freezer at -20° C., butdeposition of crystals and smectic phase were not observed even after 60days.

Example 12 (Use Example 2)

A liquid crystal composition consisting of the followingcyanophenylcyclohexane group compounds:

(4-(trans-4-propylcyclohexyl)benzonitrile 30% by weight,

4-(trans-4-pentylcyclohexyl)benzonitrile 40% by weight, and

4-(trans-4-heptylcyclohexyl)benzonitrile 30% by weight,

has the following physical properties:

NI: 52.3, Δε: 10.7, Δn: 0.119, η: 21.7, and

V₁₀ in a cell thickness of 9 μm: 1.60.

A compound (No. 187) of Example 6 (15% by weight) was blended with theabove composition (85% by weight), to prepare a nematic liquid crystalcomposition (b). The physical properties of this composition were asfollows:

NI: 55.6, Δε: 17.5, Δn: 0.121, η: 33.1 and

V₁₀ in a cell thickness of 8.8 μm: 1.06.

This composition was allowed to stand in a freezer at -20° C., butdeposition of crystals and smectic phase were not observed even after 60days.

Example 13 (Use Example 3)

The physical properties of nematic liquid crystal composition ofcomposition example 19 were as follows:

NI: 92.1, Δn: 0.143, η: 32.7, and V₁₀ in a cell

thickness of 8.9 μm: 1.20.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 14 (Use Example 4)

The physical properties of nematic liquid crystal composition ofcomposition example 29 were as follows:

NI: 79.1, Δε: 11.9, Δn: 0.139, η: 25.8, Vth: 1.32.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 15 (Use Example 5)

The physical properties of nematic liquid crystal composition ofcomposition example 30 were as follows:

NI: 97.2, Δε: 21.1, Δn: 0.155, η: 25.3, Vth: 1.22.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 16 (Use Example 6)

The physical properties of nematic liquid crystal composition ofcomposition example 31 were as follows:

NI: 98.5, Δε: 11.8, Δn: 0.139, η: 36.2, Vth: 1.63.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 17 (Use Example 7)

The physical properties of nematic liquid crystal composition ofcomposition example 32 were as follows:

NI: 81.9, Δε: 22.6, Δn: 0.147, η: 49.3, Vth: 1.07.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 18 (Use Example 8)

The physical properties of nematic liquid crystal composition ofcomposition example 33 were as follows:

NI: 81.0, Δε: 11.1, Δn: 0.126, η: 35.8, Vth: 1.53.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 19 (Use Example 9)

The physical properties of nematic liquid crystal composition ofcomposition example 34 were as follows:

NI: 76.7, Δε: 12.8, Δn: 0.123, η: 28.8, Vth: 1.58.

This composition was allowed to stand In a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 20 (Use Example 10)

The physical properties of nematic liquid crystal composition ofcomposition example 35 were as follows:

NI: 85.0, Δε: 12.7, Δn: 0.141, η: 29.3, Vth: 1.51.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 21 (Use Example 11)

The physical properties of nematic liquid crystal composition ofcomposition example 36 were as follows:

NI: 74.9, Δε: 13.6, Δn: 0.131, η: 45.3, Vth: 1.33.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 22 (Use Example 12)

The physical properties of nematic liquid crystal composition ofcomposition example 37 were as follows:

NI: 76.1, Δε: 13.3, Δn: 0.135, η: 23.4, Vth: 1.24.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 23 (Use Example 13)

The physical properties of nematic liquid crystal composition ofcomposition example 38 were as follows:

NI: 92.2, Δε: 10.5, Δn: 0.163, η: 18.6, Vth: 1.68.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 24 (Use Example 14)

The physical properties of nematic liquid crystal composition ofcomposition example 39 were as follows:

NI: 89.3, Δε: 16.8, Δn: 0.141, η: 29.6, Vth: 1.30.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 25 (Use Example 15)

The physical properties of nematic liquid crystal composition ofcomposition example 40 were as follows:

NI: 92.1, Δε: 17.1, Δn: 0.143, η: 32.7, Vth: 1.20.

This composition was allowed to stand in a freezer at -20° C., but anydeposition of crystals and smectic phase were not observed even after 60days.

Example 26

With regard to the liquid crystal composition (a) obtained in Example11, and Comparative liquid crystal composition (c) obtained in the samemanner as in Example 11 except that 3,5-difluoro-4-cyanophenyl═4-pentylbenzoate outside the range of the present invention was used in place ofNo. 4 compound, the respective temperature changes in the thresholdvoltages were measured. The results are shown in FIG. 1.

In addition, in the figure, the longitudinal axis refers to V₁₀ (V), andthe lateral axis refers to a value (°C.) obtained by substracting theclearing point (NI) of the liquid crystal composition from the measuredtemperature (T).

As apparent from the figure, the change in the threshold voltage withinthe measured temperatures, is 6.3 mV/°C. in the case of the liquidcrystal composition (a) of the present invention, whereas it is 7.3mV/°C. in the case of the liquid crystal composition (c); thus it wasfound that the temperature change of the liquid crystal composition ofthe present invention was smaller. Accordingly, it is possible toprovide a liquid crystal display element having a higher grade.

Example 27

With regard to the liquid crystal composition (b) of the presentinvention obtained in Example 12, and a comparative liquid crystalcomposition (d) obtained in the same manner as in Example 12 except that3,5-difluoro-4-cyanophenyl 4-(trans-4-butylcyclohexyl)benzoate outsidethe range of the present invention was used in place of compound No.187, the respective temperature changes in the threshold voltages weremeasured. The results are shown in FIG. 2.

As apparent from the figure, the change in the threshold voltage withinthe measured temperatures, is 5.3 mV/°C. in the case of the liquidcrystal composition (b) of the present invention, whereas it is 6.3mV/°C. in the case of the liquid crystal composition (d); thus it wasfound that the temperature change of the liquid crystal composition ofthe present invention was smaller, as in Example 26. Accordingly, it ispossible to provide a liquid crystal display element having a highergrade.

Effectiveness of the Invention

As seen from the foregoing any of the compounds of the present inventionhave a large dielectric anisotropy value, a small change in thethreshold voltage value depending upon temperatures, and an improvedsolubility in other liquid crystal materials at lower temperatures.

Accordingly, when the compound of the present invention is used as acomponent of liquid crystal compositions, it is characterized byexhibiting a superior solubility in other liquid crystal materials, andwhen six-membered ring, substituent and/or bonding group asmolecule-constituting elements are adequately selected, it is possibleto provide novel liquid crystal compositions having desired physicalproperties.

What we claim is:
 1. A liquid crystalline compound expressed by theformula (1): ##STR1084## wherein R represents an alkyl group of 1 to 10carbon atoms; l represents an integer of 1 to 9; m and n eachindependently represents 0 or 1; o represents 1; A₁, A₂ and A₃ eachindependently represents trans-1,4-cyclohexylene group, 1,4-phenylenegroup, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group or1,3-dioxane-2,5-diyl group, one or more hydrogen atoms on the rings ofwhich groups may be replaced by F; Z₁, Z₂ and Z₃ each independentlyrepresent --COO--, --(CH₂)₂ -- or a covalent bond, at least one of whichrepresents --COO--; X represents CN, CF₃, CF₂ H, CFH₂, OCF₃ or OCF₂ H;Y₁ represents H or F, but when X represents CN, Y₁ represents F; and Y₂represents F.
 2. A liquid crystalline compound according to claim 1,wherein m represents 1; n represents 0; A₁ represents 1,4-phenylenegroup, one or more hydrogen atoms on the ring of which group may bereplaced by F; and Z₁ represents --COO--.
 3. A liquid crystallinecompound according to claim 1, wherein m and n each represent 1; A₁ andA₂ each represent 1,4-phenylene group, one or more hydrogen atoms on thering of which group may be replaced by F; and Z₁ represents --COO--. 4.A liquid crystalline compound according to claim 1, wherein m and n eachrepresent 1; A₁ represents 1,4-phenylene group, one or more hydrogenatoms on the ring of which group may be replaced by F; A₂ representstrans-1,4-cyclohexylene group; and Z₁ represents --COO--.
 5. A liquidcrystalline compound according to claim 1, wherein m and n eachrepresent 1; A₁ represents trans-1,4-cyclohexylene group; A₂ represents1,4-phenylene group, one or more hydrogen atoms on the ring of whichgroup may be replaced by F; and Z₂ represents --COO--.
 6. A liquidcrystalline compound according to claim 1, wherein m and n eachrepresent 1; A₁ and A₂ each represent 1,4-phenylene group, one or morehydrogen atoms on the ring of which group may be replaced by F; and Z₂represents --COO--.
 7. A liquid crystalline compound according to claim1, wherein m and n each represent 1; A₁ representstrans-1,4-cyclohexylene; A₂ represents 1,4-phenylene group, one or morehydrogen atoms on the ring of which group may be replaced by F; Z₁represents --(CH₂)--; and Z₂ represents --COO--.
 8. A liquid crystallinecompound according to claim 1, wherein m and n each represent 1; A₁represents trans-1,4-cyclohexylene group; A₂ and A₃ each represent1,4-phenylene group, one or more hydrogen atoms on the ring of whichgroup may be replaced by F; Z₁ and Z₃ each represent a covalent bond;and Z₂ represents --COO--.
 9. A liquid crystal composition comprising asa first component, at least one member of the liquid crystallinecompounds set forth in any one of claims 2 to 8 or 1, and as a secondcomponent, at least one member selected from the group consisting ofcompounds expressed by the following formulas (2), (3) and (4):##STR1085## wherein R₁ represents an alkyl group of 1 to 10 carbonatoms; X₁ represents F, Cl, OCF₃, OCF₂ H, CF₃, CF₂ H or CFH₂ ; L₁, L₂,L₃ and L₄ each independently represent H or F; Z₄ and Z₅ eachindependently represent --(CH₂)₂ --, --CH═CH-- or a covalent bond; and arepresents 1 or
 2. 10. A liquid crystal composition comprising at leasttwo compounds, at least one compound being a liquid crystalline compoundset forth in any one of claims 2 to 8 or
 1. 11. A liquid crystal displayelement comprising of a liquid crystal composition set forth in claim10.
 12. A liquid crystal composition, comprising as a first component,at least one member of the liquid crystalline compounds set forth in anyone of claims 2 to 8 or 1, as a part of a second component, at least onemember selected from the group consisting of the compounds expressed bythe following formulas (2), (3) and (4): ##STR1086## wherein R₁represents an alkyl group of 1 to 10 carbon atoms; X₁ represents F, Cl,OCF₃, OCF₂ H, CF₃, CF₂ H or CFH₂ ; L₁, L₂, L₃ and L₄ each independentlyrepresent H or F; Z₄ and Z₅ each independently represent --(CH₂)₂ --,--CH═CH-- or a covalent bond; and a represents 1 or 2; and as anotherpart of the second component, at least one member selected from thegroup consisting of the compounds expressed by the following formulas(5), (6), (7), (8) and (9): ##STR1087## wherein, in the formula (5), R₂represents F, an alkyl group of 1 to 10 carbon atoms or an alkenyl groupof 2 to 10 carbon atoms, and any methylene group (--CH₂ --) in the alkylgroup or the alkenyl group may be replaced by an oxygen atom (--O--),but two or more adjacent methylene groups are not replaced by oxygenatoms; ring A represents trans-1,4-cyclohexylene group, 1,4-phenylenegroup, pyrimidine-2,5-diyl group or 1,3-dioxane-2,5-diyl group; ring Brepresents trans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring C represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₆ represents --(CH₂)₂ --, --COO-- or acovalent bond; L₅ and L₆ each independently represent H or F; b and ceach independently represent 0 or 1,in the formula (6), R₃ represents analkyl group of 1 to 10 carbon atoms; L₇ represents H or F; and drepresents 0 or 1, in the formula (7), R₄ represents an alkyl group of 1to 10 carbon atoms; rings D and E each independently representtrans-1,4-cyclohexylene group or 1,4-phenylene group; Z₇ and Z₈ eachindependently represent --COO-- or a covalent bond; Z₉ represents--COO-- or --C.tbd.C--; L₈ and L₉ each independently represent H or F;X₂ represents F, OCF₃, OCF₂ H, CF₃, CF₂ H or CFH₂, but when X₂represents OCF₃, OCF₂ H₂, CF₃, CF₂ H or CFH₂, L₈ and L₉ both representH; and e, f and g each independently represent 0 or 1, in the formula(8), R₅ and R₆ each independently represent an alkyl group of 1 to 10carbon atoms or an alkenyl group of 2 to 10 carbon atoms, and anymethylene group (--CH₂ --) in the alkyl group or the alkenyl group maybe replaced by an oxygen atom (--O--), but two or more adjacentmethylene groups are not replaced by oxygen atoms; ring G representstrans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring H represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₁₀ represents --C.tbd.C--, --COO--,--(CH₂)₂ --, --CH═CH--C.tbd.C-- or a covalent bond; and Z₁₁ represents--COO-- or a covalent bond, and in the formula (9), R₇ and R8 eachindependently represent an alkyl group of 1 to 10 carbon atoms or analkenyl group of 2 to 10 carbon atoms, and any methylene group (--CH₂--) in the alkyl group or the alkenyl group may be replaced by an oxygenatom (--O--), but two or more adjacent methylene groups are not replacedby oxygen atoms; ring I represents trans-1,4-cyclohexylene group,1,4-phenylene group or pyrimidine-2,5-diyl group; ring J representstrans-1,4-cyclohexylene group, or 1,4-phenylene group, orpyrimidine-2,5-diyl group, one or more hydrogen atoms on the rings ofwhich groups may be replaced by F, ring K representstrans-1,4-cyclohexylene group or 1,4-phenylene group; Z₁₂ and Z₁₄ eachindependently represent --COO--, --(CH₂)₂ -- or a covalent bond; Z₁₃represents --CH═CH--, --C.tbd.C--, --COO-- or a covalent bond; and hrepresents 0 or
 1. 13. A liquid crystal display element comprising aliquid crystal composition set forth in claim
 9. 14. A liquid crystalcomposition comprising as a first component, at least one member of theliquid crystalline compounds set forth in any one of claims 2 to 8 or 1,and as a second component, at least one member selected from the groupconsisting of compounds expressed by the following formulas (5), (6),(7), (8) and (9): ##STR1088## wherein, in the formula (5), R₂ representsF, an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10carbon atoms, and any methylene group (--CH₂ --) in the alkyl group orthe alkenyl group may be replaced by an oxygen atom (--O--), but two ormore adjacent methylene groups are not replaced by oxygen atoms; ring Arepresents trans-1,4-cyclohexylene group, 1,4-phenylene group,pyrimidine-2,5-diyl group or 1,3-dioxane-2,5-diyl group; ring Brepresents trans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring C represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₆ represents --(CH₂)₂ --, --COO-- or acovalent bond; L₅ and L₆ each independently represent H or F; b and ceach independently represent 0 or 1,in the formula (6), R₃ represents analkyl group of 1 to 10 carbon atoms; L₇ represents H or F; and drepresents 0 or 1, in the formula (7), R₄ represents an alkyl group of 1to 10 carbon atoms; rings D and E each independently representtrans-1,4-cyclohexylene group or 1,4-phenylene group; Z₇ and Z₈ eachindependently represent --COO-- or a covalent bond; Z₉ represents--COO-- or --C.tbd.C--; L₈ and L₉ each independently represent H or F;X₂ represents F, OCF₃, OCF₂ H, CF₃, CF₂ H or CFH₂, but when X₂represents OCF₃, OCF₂ H₂, CF₃, CF₂ H or CFH₂, L₈ and L₉ both representH; and e, f and g each independently represent 0 or 1, in the formula(8), R₅ and R₆ each independently represent an alkyl group of 1 to 10carbon atoms or an alkenyl group of 2 to 10 carbon atoms, and anymethylene group (--CH₂ --) in the alkyl group or the alkenyl group maybe replaced by an oxygen atom (--O--), but two or more adjacentmethylene groups are not replaced by oxygen atoms; ring G representstrans-1,4-cyclohexylene group, 1,4-phenylene group orpyrimidine-2,5-diyl group; ring H represents trans-1,4-cyclohexylenegroup or 1,4-phenylene group; Z₁₀ represents --C.tbd.C--, --COO--,--(CH₂)₂ --, --CH═CH--C.tbd.C-- or a covalent bond; and Z₁₁ represents--COO-- or a covalent bond, and in the formula (9), R₇ and R₈ eachindependently represent an alkyl group of 1 to 10 carbon atoms or analkenyl group of 2 to 10 carbon atoms, and any methylene group (--CH₂--) in the alkyl group or the alkenyl group may be replaced by an oxygenatom (--O--), but two or more adjacent methylene groups are not replacedby oxygen atoms; ring I represents trans-1,4-cyclohexylene group,1,4-phenylene group or pyrimidine-2,5-diyl group; ring J representstrans-1,4-cyclohexylene group, or 1,4-phenylene group, orpyrimidine-2,5-diyl group, one or more hydrogen atoms on the rings ofwhich groups may be replaced by F, ring K representstrans-1,4-cyclohexylene group or 1,4-phenylene group; Z₁₂ and Z₁₄ eachindependently represent --COO--, --(CH₂)₂ -- or a covalent bond; Z₁₃represents --CH═CH--, --C.tbd.C--, --COO-- or a covalent bond; and hrepresents 0 or
 1. 15. A liquid crystal display element comprising aliquid crystal composition set forth in claim
 14. 16. A liquid crystaldisplay element comprising a liquid crystal composition set forth inclaim
 12. 17. A phenol derivative expressed by the formula (1-a):##STR1089## wherein A₃ represents trans-1,4-cyclohexylene group or1,4-phenylene group, one or more hydrogen atoms on the ring of whichgroup may be replaced by F, X represents CF₂ H, CFH₂, OCF₃ or OCF₂ H, Y₁represents H or F, and o represents an integer of 0 or 1.